Curable composition and resin for treatment of a subterranean formation

ABSTRACT

Various embodiments disclosed relate to a curable composition and resin for treatment of a subterranean formation. In various embodiments, the present invention provides a method of treating a subterranean formation. The method can include placing in a subterranean formation a curable composition. The curable composition can include an epoxy silane monomer, a hardener, and carrier fluid. The curable composition can include an epoxy monomer, an amine silane hardener, and carrier fluid. The method can also include curing the curable composition to form an epoxy silane resin.

BACKGROUND

Epoxy resins have been used as alternatives to cement for remediation ofwellbores. These resins flow easily into small cracks and microannuli,which are inaccessible to particle-based fluids, such as Portlandcement. However, most epoxy resins have a low temperature threshold,which is typically related to the glass transition temperature (T_(g))of the polymer. At temperatures over about 400° F., most epoxy resinsare thermally unstable. As an alternative to epoxy resins, siliconresins have also been employed due to their temperature stability.However, silicon resins have poor adhesion properties, hindering theiruse for the remediation of wellbores.

Separately, epoxy resins and silicon resins often require the use ofcuring agents. Unfortunately, epoxy resin-curing agents and siliconresin-curing agents often interfere with each other making thesimultaneous use of epoxy resins and silicon resins difficult. Further,the use of epoxy resin-curing agents and silicon resin-curing agents,such as platinum based curing agents, adds additional costs when epoxyresins or silicon resins are used.

Additionally, furan resins have been employed due to their extremetemperature stability. However, most furan resins are typically brittleand do not have desirable adhesion to casing.

BRIEF DESCRIPTION OF THE FIGURES

The drawings illustrate generally, by way of example, but not by way oflimitation, various embodiments discussed in the present document.

FIG. 1 illustrates a system or apparatus for delivering a composition toa subterranean formation, in accordance with various embodiments.

FIG. 2 illustrates a thermogram of an epoxy silane resin formed fromSilquest® A-187 (10 g), Jeffamine® D230 (2.7 g) and water (2.8 g) (e.g.,Sample 2 of Example 2) in accordance with various embodiments.

FIG. 3 illustrates a thermogram of an epoxy resin formed fromcyclohexanedimethanol diglycidyl ether (20 g) and Jeffamine® D230 (9.0g) (e.g., Sample 5 of Example 2).

DETAILED DESCRIPTION OF THE INVENTION

Reference will now be made in detail to certain embodiments of thedisclosed subject matter, examples of which are illustrated in part inthe accompanying drawings. While the disclosed subject matter will bedescribed in conjunction with the enumerated claims, it will beunderstood that the exemplified subject matter is not intended to limitthe claims to the disclosed subject matter.

Values expressed in a range format should be interpreted in a flexiblemanner to include not only the numerical values explicitly recited asthe limits of the range, but also to include all the individualnumerical values or sub-ranges encompassed within that range as if eachnumerical value and sub-range is explicitly recited. For example, arange of “about 0.1% to about 5%” or “about 0.1% to 5%” should beinterpreted to include not just about 0.1% to about 5%, but also theindividual values (e.g., 1%, 2%, 3%, and 4%) and the sub-ranges (e.g.,0.1% to 0.5%, 1.1% to 2.2%, 3.3% to 4.4%) within the indicated range.The statement “about X to Y” has the same meaning as “about X to aboutY,” unless indicated otherwise. Likewise, the statement “about X, Y, orabout Z” has the same meaning as “about X, about Y, or about Z,” unlessindicated otherwise.

In this document, the terms “a,” “an,” or “the” are used to include oneor more than one unless the context clearly dictates otherwise. The term“or” is used to refer to a nonexclusive “or” unless otherwise indicated.The statement “at least one of A and B” has the same meaning as “A, B,or A and B.” In addition, it is to be understood that the phraseology orterminology employed herein, and not otherwise defined, is for thepurpose of description only and not of limitation. Any use of sectionheadings is intended to aid reading of the document and is not to beinterpreted as limiting; information that is relevant to a sectionheading may occur within or outside of that particular section. A commacan be used as a delimiter or digit group separator to the left or rightof a decimal mark; for example, “0.000,1” is equivalent to “0.0001.”

In the methods of manufacturing described herein, the acts can becarried out in any order without departing from the principles of theinvention, except when a temporal or operational sequence is explicitlyrecited. Furthermore, specified acts can be carried out concurrentlyunless explicit claim language recites that they be carried outseparately. For example, a claimed act of doing X and a claimed act ofdoing Y can be conducted simultaneously within a single operation, andthe resulting process will fall within the literal scope of the claimedprocess.

The term “about” as used herein can allow for a degree of variability ina value or range, for example, within 10%, within 5%, or within 1% of astated value or of a stated limit of a range.

The term “substantially” as used herein refers to a majority of, ormostly, as in at least about 50%, 60%, 70%, 80%, 90%, 95%, 96%, 97%,98%, 99%, 99.5%, 99.9%, 99.99%, or at least about 99.999% or more.

The term “organic group” as used herein refers to but is not limited toany carbon-containing functional group. For example, anoxygen-containing group such as an alkoxy group, aryloxy group,aralkyloxy group, oxo(carbonyl) group, a carboxyl group including acarboxylic acid, carboxylate, and a carboxylate ester; asulfur-containing group such as an alkyl and aryl sulfide group; andother heteroatom-containing groups. Non-limiting examples of organicgroups include OR, OOR, OC(O)N(R)₂, CN, CF₃, OCF₃, R, C(O),methylenedioxy, ethylenedioxy, N(R)₂, SR, SOR, SO₂R, SO₂N(R)₂, SO₃R,C(O)R, C(O)C(O)R, C(O)CH₂C(O)R, C(S)R, C(O)OR, OC(O)R, C(O)N(R)₂,OC(O)N(R)₂, C(S)N(R)₂, (CH₂)₀₋₂N(R)C(O)R, (CH₂)₀₋₂N(R)N(R)₂,N(R)N(R)C(O)R, N(R)N(R)C(O)OR, N(R)N(R)CON(R)₂, N(R)SO₂R, N(R)SO₂N(R)₂,N(R)C(O)OR, N(R)C(O)R, N(R)C(S)R, N(R)C(O)N(R)₂, N(R)C(S)N(R)₂,N(COR)COR, N(OR)R, C(═NH)N(R)₂, C(O)N(OR)R, or C(═NOR)R, wherein R canbe hydrogen (in examples that include other carbon atoms) or acarbon-based moiety, and wherein the carbon-based moiety can itself befurther substituted.

The term “substituted” as used herein refers to an organic group asdefined herein or molecule in which one or more hydrogen atoms containedtherein are replaced by one or more non-hydrogen atoms. The term“functional group” or “substituent” as used herein refers to a groupthat can be or is substituted onto a molecule or onto an organic group.Examples of substituents or functional groups include, but are notlimited to, a halogen (e.g., F, Cl, Br, and I); an oxygen atom in groupssuch as hydroxy groups, alkoxy groups, aryloxy groups, aralkyloxygroups, oxo(carbonyl) groups, carboxyl groups including carboxylicacids, carboxylates, and carboxylate esters; a sulfur atom in groupssuch as thiol groups, alkyl and aryl sulfide groups, sulfoxide groups,sulfone groups, sulfonyl groups, and sulfonamide groups; a nitrogen atomin groups such as amines, hydroxyamines, nitriles, nitro groups,N-oxides, hydrazides, azides, and enamines; and other heteroatoms invarious other groups. Non-limiting examples of substituents that can bebonded to a substituted carbon (or other) atom include F, Cl, Br, I, OR,OC(O)N(R)₂, CN, NO, NO₂, ONO₂, azido, CF₃, OCF₃, R, O (oxo), S (thiono),C(O), S(O), methylenedioxy, ethylenedioxy, N(R)₂, SR, SOR, SO₂R,SO₂N(R)₂, SO₃R, C(O)R, C(O)C(O)R, C(O)CH₂C(O)R, C(S)R, C(O)OR, OC(O)R,C(O)N(R)₂, OC(O)N(R)₂, C(S)N(R)₂, (CH₂)₀₋₂N(R)C(O)R, (CH₂)₀₋₂N(R)N(R)₂,N(R)N(R)C(O)R, N(R)N(R)C(O)OR, N(R)N(R)CON(R)₂, N(R)SO₂R, N(R)SO₂N(R)₂,N(R)C(O)OR, N(R)C(O)R, N(R)C(S)R, N(R)C(O)N(R)₂, N(R)C(S)N(R)₂,N(COR)COR, N(OR)R, C(═NH)N(R)₂, C(O)N(OR)R, or C(═NOR)R, wherein R canbe hydrogen or a carbon-based moiety, and wherein the carbon-basedmoiety can itself be further substituted; for example, R can behydrogen, alkyl, acyl, cycloalkyl, aryl, aralkyl, heterocyclyl,heteroaryl, or heteroarylalkyl.

The term “alkyl” as used herein refers to straight chain and branchedalkyl groups and cycloalkyl groups having from 1 to 40 carbon atoms, 1to about 20 carbon atoms, 1 to 12 carbons or, in some embodiments, from1 to 8 carbon atoms. Examples of straight chain alkyl groups includethose with from 1 to 8 carbon atoms such as methyl, ethyl, n-propyl,n-butyl, n-pentyl, n-hexyl, n-heptyl, and n-octyl groups. Examples ofbranched alkyl groups include, but are not limited to, isopropyl,iso-butyl, sec-butyl, t-butyl, neopentyl, isopentyl, and2,2-dimethylpropyl groups. As used herein, the term “alkyl” encompassesn-alkyl, isoalkyl, and anteisoalkyl groups as well as other branchedchain forms of alkyl. Representative substituted alkyl groups can besubstituted one or more times with any of the groups listed herein, forexample, amino, hydroxy, cyano, carboxy, nitro, thio, alkoxy, andhalogen groups.

The term “alkenyl” as used herein refers to straight and branched chainand cyclic alkyl groups as defined herein, except that at least onedouble bond exists between two carbon atoms. Thus, alkenyl groups havefrom 2 to 40 carbon atoms, or 2 to about 20 carbon atoms, or 2 to 12carbons or, in some embodiments, from 2 to 8 carbon atoms. Examplesinclude, but are not limited to vinyl, —CH═CH(CH₃), —CH═C(CH₃)₂,—C(CH₃)═CH₂, —C(CH₃)═CH(CH₃), —C(CH₂CH₃)═CH₂, cyclohexenyl,cyclopentenyl, cyclohexadienyl, butadienyl, pentadienyl, and hexadienylamong others.

The term “alkynyl” as used herein refers to straight and branched chainalkyl groups, except that at least one triple bond exists between twocarbon atoms. Thus, alkynyl groups have from 2 to 40 carbon atoms, 2 toabout 20 carbon atoms, or from 2 to 12 carbons or, in some embodiments,from 2 to 8 carbon atoms. Examples include, but are not limited to—C≡CH, —C≡C(CH₃), —C≡C(CH₂CH₃), —CH₂C≡CH, —CH₂C≡C(CH₃), and—CH₂C≡C(CH₂CH₃) among others.

The term “acyl” as used herein refers to a group containing a carbonylmoiety wherein the group is bonded via the carbonyl carbon atom. Thecarbonyl carbon atom is also bonded to another carbon atom, which can bepart of an alkyl, aryl, aralkyl cycloalkyl, cycloalkylalkyl,heterocyclyl, heterocyclylalkyl, heteroaryl, heteroarylalkyl group orthe like. In the special case wherein the carbonyl carbon atom is bondedto a hydrogen, the group is a “formyl” group, an acyl group as the termis defined herein. An acyl group can include 0 to about 12-20 or 12-40additional carbon atoms bonded to the carbonyl group. An acyl group caninclude double or triple bonds within the meaning herein. An acryloylgroup is an example of an acyl group. An acyl group can also includeheteroatoms within the meaning here. A nicotinoyl group(pyridyl-3-carbonyl) is an example of an acyl group within the meaningherein. Other examples include acetyl, benzoyl, phenylacetyl,pyridylacetyl, cinnamoyl, and acryloyl groups and the like. When thegroup containing the carbon atom that is bonded to the carbonyl carbonatom contains a halogen, the group is termed a “haloacyl” group. Anexample is a trifluoroacetyl group.

The term “cycloalkyl” as used herein refers to cyclic alkyl groups suchas, but not limited to, cyclopropyl, cyclobutyl, cyclopentyl,cyclohexyl, cycloheptyl, and cyclooctyl groups. In some embodiments, thecycloalkyl group can have 3 to about 8-12 ring members, whereas in otherembodiments the number of ring carbon atoms range from 3 to 4, 5, 6, or7. Cycloalkyl groups further include polycyclic cycloalkyl groups suchas, but not limited to, norbornyl, adamantyl, bornyl, camphenyl,isocamphenyl, and carenyl groups, and fused rings such as, but notlimited to, decalinyl, and the like. Cycloalkyl groups also includerings that are substituted with straight or branched chain alkyl groupsas defined herein. Representative substituted cycloalkyl groups can bemono-substituted or substituted more than once, such as, but not limitedto, 2,2-, 2,3-, 2,4- 2,5- or 2,6-disubstituted cyclohexyl groups ormono-, di- or tri-substituted norbornyl or cycloheptyl groups, which canbe substituted with, for example, amino, hydroxy, cyano, carboxy, nitro,thio, alkoxy, and halogen groups. The term “cycloalkenyl” alone or incombination denotes a cyclic alkenyl group.

The term “aryl” as used herein refers to cyclic aromatic hydrocarbonsthat do not contain heteroatoms in the ring. Thus aryl groups include,but are not limited to, phenyl, azulenyl, heptalenyl, biphenyl,indacenyl, fluorenyl, phenanthrenyl, triphenylenyl, pyrenyl,naphthacenyl, chrysenyl, biphenylenyl, anthracenyl, and naphthyl groups.In some embodiments, aryl groups contain about 6 to about 14 carbons inthe ring portions of the groups. Aryl groups can be unsubstituted orsubstituted, as defined herein. Representative substituted aryl groupscan be mono-substituted or substituted more than once, such as, but notlimited to, 2-, 3-, 4-, 5-, or 6-substituted phenyl or 2-8 substitutednaphthyl groups, which can be substituted with carbon or non-carbongroups such as those listed herein.

The term “aralkyl” as used herein refers to alkyl groups as definedherein in which a hydrogen or carbon bond of an alkyl group is replacedwith a bond to an aryl group as defined herein. Representative aralkylgroups include benzyl and phenylethyl groups and fused(cycloalkylaryl)alkyl groups such as 4-ethyl-indanyl. Aralkenyl groupsare alkenyl groups as defined herein in which a hydrogen or carbon bondof an alkyl group is replaced with a bond to an aryl group as definedherein.

The term “heterocyclyl” as used herein refers to aromatic andnon-aromatic ring compounds containing three or more ring members, ofwhich one or more is a heteroatom such as, but not limited to, N, O, andS. Thus, a heterocyclyl can be a cycloheteroalkyl, or a heteroaryl, orif polycyclic, any combination thereof. In some embodiments,heterocyclyl groups include 3 to about 20 ring members, whereas othersuch groups have 3 to about 15 ring members. A heterocyclyl groupdesignated as a C₂-heterocyclyl can be a 5-ring with two carbon atomsand three heteroatoms, a 6-ring with two carbon atoms and fourheteroatoms and so forth. Likewise a C₄-heterocyclyl can be a 5-ringwith one heteroatom, a 6-ring with two heteroatoms, and so forth. Thenumber of carbon atoms plus the number of heteroatoms equals the totalnumber of ring atoms. A heterocyclyl ring can also include one or moredouble bonds. A heteroaryl ring is an embodiment of a heterocyclylgroup. The phrase “heterocyclyl group” includes fused ring speciesincluding those that include fused aromatic and non-aromatic groups.

The term “heterocyclylalkyl” as used herein refers to alkyl groups asdefined herein in which a hydrogen or carbon bond of an alkyl group asdefined herein is replaced with a bond to a heterocyclyl group asdefined herein. Representative heterocyclyl alkyl groups include, butare not limited to, furan-2-yl methyl, furan-3-yl methyl, pyridine-3-ylmethyl, tetrahydrofuran-2-yl ethyl, and indol-2-yl propyl.

The term “heteroarylalkyl” as used herein refers to alkyl groups asdefined herein in which a hydrogen or carbon bond of an alkyl group isreplaced with a bond to a heteroaryl group as defined herein.

The term “alkoxy” as used herein refers to an oxygen atom connected toan alkyl group, including a cycloalkyl group, as are defined herein.Examples of linear alkoxy groups include but are not limited to methoxy,ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, and the like. Examples ofbranched alkoxy include but are not limited to isopropoxy, sec-butoxy,tert-butoxy, isopentyloxy, isohexyloxy, and the like. Examples of cyclicalkoxy include but are not limited to cyclopropyloxy, cyclobutyloxy,cyclopentyloxy, cyclohexyloxy, and the like. An alkoxy group can includeone to about 12-20 or about 12-40 carbon atoms bonded to the oxygenatom, and can further include double or triple bonds, and can alsoinclude heteroatoms. For example, an allyloxy group is an alkoxy groupwithin the meaning herein. A methoxyethoxy group is also an alkoxy groupwithin the meaning herein, as is a methylenedioxy group in a contextwhere two adjacent atoms of a structure are substituted therewith.

The term “amine” as used herein refers to primary, secondary, andtertiary amines having, e.g., the formula N(group)₃ wherein each groupcan independently be H or non-H, such as alkyl, aryl, and the like.Amines include but are not limited to R—NH₂, for example, alkylamines,arylamines, alkylarylamines; R₂NH wherein each R is independentlyselected, such as dialkylamines, diarylamines, aralkylamines,heterocyclylamines and the like; and R₃N wherein each R is independentlyselected, such as trialkylamines, dialkylarylamines, alkyldiarylamines,triarylamines, and the like. The term “amine” also includes ammoniumions as used herein.

The term “amino group” as used herein refers to a substituent of theform —NH₂, —NHR, —NR₂, —NR₃ ⁺, wherein each R is independently selected,and protonated forms of each, except for —NR₃ ⁺, which cannot beprotonated. Accordingly, any compound substituted with an amino groupcan be viewed as an amine. An “amino group” within the meaning hereincan be a primary, secondary, tertiary, or quaternary amino group. An“alkylamino” group includes a monoalkylamino, dialkylamino, andtrialkylamino group.

The terms “halo,” “halogen,” or “halide” group, as used herein, bythemselves or as part of another substituent, mean, unless otherwisestated, a fluorine, chlorine, bromine, or iodine atom.

The term “haloalkyl” group, as used herein, includes mono-halo alkylgroups, poly-halo alkyl groups wherein all halo atoms can be the same ordifferent, and per-halo alkyl groups, wherein all hydrogen atoms arereplaced by halogen atoms, such as fluoro. Examples of haloalkyl includetrifluoromethyl, 1,1-dichloroethyl, 1,2-dichloroethyl,1,3-dibromo-3,3-difluoropropyl, perfluorobutyl, and the like.

The term “hydrocarbon” as used herein refers to a functional group ormolecule that includes carbon and hydrogen atoms. The term can alsorefer to a functional group or molecule that normally includes bothcarbon and hydrogen atoms but wherein all the hydrogen atoms aresubstituted with other functional groups.

As used herein, the term “hydrocarbyl” as used herein refers to afunctional group derived from a straight chain, branched, or cyclichydrocarbon, and can be alkyl, alkenyl, alkynyl, aryl, cycloalkyl, acyl,or any combination thereof.

The term “solvent” as used herein refers to a liquid that can dissolve asolid, liquid, or gas. Non-limiting examples of solvents are silicones,organic compounds, water, alcohols, ionic liquids, and supercriticalfluids.

The term “silane” as used herein refers to a silicon atom with anysuitable substituent thereon, including hydrocarbyl, hydrocarbyloxy, andhydroxy, such as silanols, siloxanes, and polysiloxanes and theirreaction products and derivatives which can be “silane” mixtures.

The term “epoxy monomer” as used herein refers to molecules that includeone or more epoxy functional group. Non-limiting examples of epoxymonomers include polyethylene glycol diglycidyl ether,cyclohexanedimethanol diglycidyl ether, trimethylolpropane tricglycidylether, and epoxy silane monomers.

Polyethylene glycol diglycidyl ether has the structure

Cyclohexanedimethanol diglycidyl ether has the structure

Trimethylolpropane triglycidyl ether has the structure

The term “room temperature” as used herein refers to a temperature ofabout 15° C. to 28° C.

The term “standard temperature and pressure” as used herein refers to20° C. and 101 kPa.

As used herein, “degree of polymerization” is the number of repeatingunits in a polymer.

As used herein, the term “polymer” refers to a molecule having at leastone repeating unit and can include copolymers.

The term “glass transition temperature” or “T_(g)” as used herein refersgenerally to the temperature below which a material is relatively hardand/or brittle.

The term “copolymer” as used herein refers to a polymer that includes atleast two different repeating units. A copolymer can include anysuitable number of repeating units.

The term “downhole” as used herein refers to under the surface of theearth, such as a location within or fluidly connected to a wellbore.

As used herein, the term “drilling fluid” refers to fluids, slurries, ormuds used in drilling operations downhole, such as during the formationof the wellbore.

As used herein, the term “stimulation fluid” refers to fluids orslurries used downhole during stimulation activities of the well thatcan increase the production of a well, including perforation activities.In some examples, a stimulation fluid can include a fracturing fluid oran acidizing fluid.

As used herein, the term “clean-up fluid” refers to fluids or slurriesused downhole during clean-up activities of the well, such as anytreatment to remove material obstructing the flow of desired materialfrom the subterranean formation. In one example, a clean-up fluid can bean acidification treatment to remove material formed by one or moreperforation treatments. In another example, a clean-up fluid can be usedto remove a filter cake.

As used herein, the term “fracturing fluid” refers to fluids or slurriesused downhole during fracturing operations.

As used herein, the term “spotting fluid” refers to fluids or slurriesused downhole during spotting operations, and can be any fluid designedfor localized treatment of a downhole region. In one example, a spottingfluid can include a lost circulation material for treatment of aspecific section of the wellbore, such as to seal off fractures in thewellbore and prevent sag. In another example, a spotting fluid caninclude a water control material. In some examples, a spotting fluid canbe designed to free a stuck piece of drilling or extraction equipment,can reduce torque and drag with drilling lubricants, preventdifferential sticking, promote wellbore stability, and can help tocontrol mud weight.

As used herein, the term “completion fluid” refers to fluids or slurriesused downhole during the completion phase of a well, including cementingcompositions.

As used herein, the term “remedial treatment,” “remediation,” and“remediating” refers treatments designed to increase or maintain theproduction rate of a well, such as stimulation or clean-up treatments.

As used herein, the term “remedial treatment fluid” refers to fluids orslurries used downhole for remedial treatment of a well.

The term “consolidation,” and grammatical equivalents, as used hereinrefers to controlling the undesirable production of sand, clays, andother fines from subterranean formations. Consolidation can bindtogether the sand, clays, and other fines in the subterranean formationwhile maintaining sufficient permeability to achieve viable productionrates.

As used herein, the term “abandonment fluid” refers to fluids orslurries used downhole during or preceding the abandonment phase of awell.

As used herein, the term “acidizing fluid” refers to fluids or slurriesused downhole during acidizing treatments. In one example, an acidizingfluid is used in a clean-up operation to remove material obstructing theflow of desired material, such as material formed during a perforationoperation. In some examples, an acidizing fluid can be used for damageremoval.

As used herein, the term “cementing fluid” refers to fluids or slurriesused during cementing operations of a well. For example, a cementingfluid can include an aqueous mixture including at least one of cementand cement kiln dust.

As used herein, the term “water control material” refers to a solid orliquid material that interacts with aqueous material downhole, such thathydrophobic material can more easily travel to the surface and such thathydrophilic material (including water) can less easily travel to thesurface. A water control material can be used to treat a well to causethe proportion of water produced to decrease and to cause the proportionof hydrocarbons produced to increase, such as by selectively bindingtogether material between water-producing subterranean formations andthe wellbore while still allowing hydrocarbon-producing formations tomaintain output.

As used herein, the term “packer fluid” refers to fluids or slurriesthat can be placed in the annular region of a well between tubing andouter casing above a packer. In various examples, the packer fluid canprovide hydrostatic pressure in order to lower differential pressureacross the sealing element, lower differential pressure on the wellboreand casing to prevent collapse, and protect metals and elastomers fromcorrosion.

As used herein, the term “fluid” refers to liquids and gels, unlessotherwise indicated.

As used herein, the term “subterranean material” or “subterraneanformation” refers to any material under the surface of the earth,including under the surface of the bottom of the ocean. For example, asubterranean formation or material can be any section of a wellbore andany section of a subterranean petroleum- or water-producing formation orregion in fluid contact with the wellbore. Placing a material in asubterranean formation can include contacting the material with anysection of a wellbore or with any subterranean region in fluid contacttherewith. Subterranean materials can include any materials placed intothe wellbore such as cement, drill shafts, liners, tubing, casing, orscreens; placing a material in a subterranean formation can includecontacting with such subterranean materials. In some examples, asubterranean formation or material can be any below-ground region thatcan produce liquid or gaseous petroleum materials, water, or any sectionbelow-ground in fluid contact therewith. For example, a subterraneanformation or material can be at least one of an area desired to befractured, a fracture or an area surrounding a fracture, and a flowpathway or an area surrounding a flow pathway, wherein a fracture or aflow pathway can be optionally fluidly connected to a subterraneanpetroleum- or water-producing region, directly or through one or morefractures or flow pathways.

As used herein, “treatment of a subterranean formation” can include anyactivity directed to extraction of water or petroleum materials from asubterranean petroleum- or water-producing formation or region, forexample, including drilling, stimulation, hydraulic fracturing,clean-up, acidizing, completion, cementing, remedial treatment,abandonment, and the like.

As used herein, a “flow pathway” downhole can include any suitablesubterranean flow pathway through which two subterranean locations arein fluid connection. The flow pathway can be sufficient for petroleum orwater to flow from one subterranean location to the wellbore orvice-versa. A flow pathway can include at least one of a hydraulicfracture, and a fluid connection across a screen, across gravel pack,across proppant, including across resin-bonded proppant or proppantdeposited in a fracture, and across sand. A flow pathway can include anatural subterranean passageway through which fluids can flow. In someembodiments, a flow pathway can be a water source and can include water.In some embodiments, a flow pathway can be a petroleum source and caninclude petroleum. In some embodiments, a flow pathway can be sufficientto divert from a wellbore, fracture, or flow pathway connected theretoat least one of water, a downhole fluid, or a produced hydrocarbon.

In various embodiments, the present invention provides a method oftreating a subterranean formation. The method includes placing in asubterranean formation a curable composition. In various embodiments,the curable composition includes an epoxy silane monomer, a hardener,and a carrier fluid. The method also includes curing the curablecomposition to form an epoxy silane resin.

In various embodiments, the present invention provides a method oftreating a subterranean formation with a curable composition thatincludes an epoxy silane monomer, a hardener, and a carrier fluid. Thecurable composition includes an epoxy silane monomer having a structurechosen from

The variable f is about 0 to about 6. The variable R^(A), at eachoccurrence, is independently chosen from —H and —CH₃, wherein the ratioof —H to —CH₃ is about 1 to 3 to about 3 to 1. The epoxy silane monomeris about 40 wt. % to about 80 wt. % of the curable composition. Thecurable composition includes a hardener having a structure chosen from

The variable n is about 1 to about 5. The hardener is about 5 wt. % toabout 50 wt. % of the curable composition. The carrier fluid includeswater and is about 1 wt. % to about 40 wt. % of the curable composition.The method also includes curing the curable composition to form an epoxysilane resin.

In various embodiments, the present invention provides a method fortreating a subterranean formation with a curable composition thatincludes an epoxy monomer, an amine silane hardener, and a carrierfluid. The method also includes curing the curable composition to forman epoxy silane resin.

In various embodiments, the present invention provides a method oftreating a subterranean formation with a curable composition thatincludes an epoxy monomer, an amine silane hardener, and a carrierfluid. The epoxy monomer is about 50 wt. % to about 70 wt. % of thecurable composition. The amine silane hardener has the structure

The amine silane hardener is about 20 wt. % to about 40 wt. % of thecurable composition. The carrier fluid includes water and is about 1 wt.% to about 40 wt. % of the curable composition.

In various embodiments, the present invention provides a systemincluding an epoxy silane resin cured reaction product of a curablecomposition including an epoxy silane monomer, a hardener, and a carrierfluid; and a subterranean formation including the resin therein.

In various embodiments, the present invention provides a systemincluding an epoxy silane resin cured reaction product of a curablecomposition including an epoxy monomer, an amine silane hardener, and acarrier fluid, and a subterranean formation including the resin therein.

In various embodiments, the present invention provides a curablecomposition for treatment of a subterranean formation. The curablecomposition includes an epoxy silane monomer, a hardener, and a carrierfluid. The epoxy silane monomer has a structure chosen from

The variable f is about 0 to about 6. The variable R^(A), at eachoccurrence, is independently chosen from —H and —CH₃, wherein the ratioof —H to —CH₃ is about 1 to 3 to about 3 to 1. The epoxy silane monomeris about 40 wt. % to about 80 wt. % of the curable composition. Thehardener has a structure chosen from

The variable n is about 1 to about 5. The hardener is about 5 wt. % toabout 50 wt. % of the curable composition. The carrier fluid includeswater and is about 1 wt. % to about 40 wt. % of the curable composition.

In various embodiments, the present invention provides a curablecomposition for treatment of a subterranean formation. The curablecomposition includes an epoxy monomer, an amine silane hardener and acarrier fluid. The epoxy monomer has the structure selected from

The variable p is about 1 to about 200. The epoxy monomer is about 50wt. % to about 70 wt. % of the curable composition. The amine silanehardener has the structure

The amine silane hardener is about 20 wt. % to about 40 wt. % of thecurable composition. The carrier fluid includes water and is about 1 wt.% to about 40 wt. % of the curable composition.

In various embodiments, the present invention provides for a method ofpreparing a curable composition for treatment of a subterraneanformation. The method includes forming a curable composition includingan epoxy silane monomer, a hardener, and a carrier fluid.

In various embodiments, the present invention provides for a method ofpreparing a curable composition for treatment of a subterraneanformation. The method includes forming a curable composition includingan epoxy monomer, an amine silane hardener, and a carrier fluid.

Various embodiments of the curable composition and method of using thesame have certain advantages over other epoxy based compositions andmethods of using the same, at least some of which are unexpected. Invarious embodiments, the curable composition can be used at highertemperatures than other epoxy compositions without sacrificingmechanical properties, adhesion properties, or stability. In variousembodiments, the increased temperature tolerance of the curablecomposition can allow for deeper and hotter wells to be serviced. Invarious embodiments, by including both epoxide and silanefunctionalities on a single monomer, segregation of epoxy and silanedomains during polymerization is reduced or eliminated, increasinghomogeneity of the resulting polymer. In various embodiments, byincluding both amine and silane functionalities on a single monomer,segregation of amine and silane domains during polymerization is reducedor eliminated, increasing homogeneity of the resulting polymer. Invarious embodiments, by including both epoxide and silanefunctionalities on a single monomer, or, alternatively, amine and silanefunctionalities on a single monomer, the costs associated withtransportation of the curable composition can be lower in comparison tothose associated with transporting compositions in which silanecontaining compounds and epoxy containing compounds are shippedseparately.

Method of Treating a Subterranean Formation.

In some embodiments, the present invention provides a method of treatinga subterranean formation. The method can include placing in asubterranean formation a curable composition including an epoxy silanemonomer, a hardener, and a carrier fluid in a subterranean formation andcuring the curable composition to form an epoxy silane resin.Alternatively, the method can include placing in a subterraneanformation a curable composition including an epoxy monomer, an aminesilane hardener, and a carrier fluid in a subterranean formation andcuring the curable composition to form an epoxy silane resin. Theplacing of the curable composition in the subterranean formation caninclude contacting the curable composition and any suitable part of thesubterranean formation, or contacting the curable composition and asubterranean material, such as any suitable subterranean material. Thesubterranean formation can be any suitable subterranean formation. Theobtaining or providing of the curable composition can occur at anysuitable time and at any suitable location. The obtaining or providingof the curable composition can occur above the surface. The obtaining orproviding of the curable composition can occur in the subterraneanformation (e.g., downhole).

The term “epoxy silane resin” as used herein refers to the productformed from the curing of any of the curable compositions disclosedherein. Curing can include, but is not limited to, ring opening epoxidepolymerization reactions as well as hydrolysis and condensation ofsilane groups to form siloxane and/or poly-siloxane groups.

In some examples, the placing of the curable composition in thesubterranean formation includes contacting the curable composition withor placing the curable composition in at least one of a fracture, atleast a part of an area surrounding a fracture, a flow pathway, an areasurrounding a flow pathway, and an area desired to be fractured. Theplacing of the curable composition in the subterranean formation can beany suitable placing and can include any suitable contacting between thesubterranean formation and the curable composition. The placing of thecurable composition in the subterranean formation can include at leastpartially depositing the curable composition in a fracture, flowpathway, or area surrounding the same.

The method can include hydraulic fracturing, such as a method ofhydraulic fracturing to generate a fracture or flow pathway. The placingof the curable composition in the subterranean formation or thecontacting of the subterranean formation and the hydraulic fracturingcan occur at any time with respect to one another; for example, thehydraulic fracturing can occur at least one of before, during, and afterthe contacting or placing. In some embodiments, the contacting orplacing occurs during the hydraulic fracturing, such as during anysuitable stage of the hydraulic fracturing, such as during at least oneof a pre-pad stage (e.g., during injection of water with no proppant,and additionally optionally mid- to low-strength acid), a pad stage(e.g., during injection of fluid only—with no proppant and with someviscosifier—such as to begin to break into an area and initiatefractures to produce sufficient penetration and width to allowproppant-laden later stages to enter), or a slurry stage of thefracturing (e.g., viscous fluid with proppant). The method can includeperforming a stimulation treatment at least one of before, during, andafter placing the curable composition in the subterranean formation inthe fracture, flow pathway, or area surrounding the same. Thestimulation treatment can be, for example, at least one of perforating,acidizing, injecting of cleaning fluids, propellant stimulation, andhydraulic fracturing. In some embodiments, the stimulation treatment atleast partially generates a fracture or flow pathway where the curablecomposition is placed or contacted, or the curable composition is placedor contacted to an area surrounding the generated fracture or flowpathway.

In some embodiments, the method can be a method of remedial treatment,consolidation, stimulation, fracturing, spotting, clean-up, completion,applying a pill, acidizing, cementing, packing, spotting, plugging forabandonment, or a combination thereof.

In various embodiments, the curable composition includes a carrierfluid. In various embodiments, the carrier fluid is water. The water canbe any suitable water. The water can include at least one of freshwater, brine, produced water, flowback water, brackish water, and seawater. The water can serve to aid in the hydrolysis and condensation ofsilane groups to form siloxane and/or poly-siloxane groups. In someembodiments, the carrier fluid can be at least one of crude oil,dipropylene glycol methyl ether, dipropylene glycol dimethyl ether,dipropylene glycol methyl ether, dipropylene glycol dimethyl ether,dimethyl formamide, diethylene glycol methyl ether, ethylene glycolbutyl ether, diethylene glycol butyl ether, butylglycidyl ether,propylene carbonate, D-limonene, a C₂-C₄₀ fatty acid C₁-C₁₀ alkyl ester(e.g., a fatty acid methyl ester), tetrahydrofurfuryl methacrylate,tetrahydrofurfuryl acrylate, 2-butoxy ethanol, butyl acetate, butyllactate, furfuryl acetate, dimethyl sulfoxide, dimethyl formamide, apetroleum distillation product of fraction (e.g., diesel, kerosene,napthas, and the like) mineral oil, a hydrocarbon oil, a hydrocarbonincluding an aromatic carbon-carbon bond (e.g., benzene, toluene), ahydrocarbon including an alpha olefin, xylenes, an ionic liquid, methylethyl ketone, an ester of oxalic, maleic or succinic acid, methanol,ethanol, propanol (iso- or normal-), butyl alcohol (iso-, tert-, ornormal-), and an aliphatic hydrocarbon (e.g., cyclohexanone, hexane). Insome embodiments, the fluid can form about 0.001 wt. % to about 99.999wt. %, about 1% to about 40%, about 5% to about 30%, about 10% to about20%, about 11% to about 19%, about 12% to about 18%, about 13% to about17%, or about 14% to about 16% of the curable composition, or a mixtureincluding the same, or about 0.001 wt. % or less, 0.01 wt. %, 0.1, 1, 2,3, 4, 5, 6, 8, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75,80, 85, 90, 95, 96, 97, 98, 99, 99.9, 99.99, or about 99.999 wt. % ormore.

In various embodiments, the method can include curing the curablecomposition to form an epoxy silane resin. The curing of the curablecomposition to form an epoxy silane resin can include ring openingepoxide polymerization reactions via reaction of the hardener with theepoxy silane monomer or epoxy monomer. The curing of the curablecomposition to form an epoxy silane resin can include the hydrolysis andcondensation of silane groups to form siloxane and/or polysiloxanegroups. The curing of the curable composition to form an epoxy silaneresin can include ring opening epoxide polymerization reactions viareaction of the hardener with the epoxy silane monomer or epoxy monomeras well as hydrolysis and condensation of silane groups to form siloxaneand/or polysiloxane groups. In various embodiments, the curing occurs atleast partially above-surface (e.g., before the placing of the curablecomposition in the subterranean formation). In some embodiments, thecuring occurs at least partially in the subterranean formation (e.g., atleast one of during and after the placing of the curable composition inthe subterranean formation).

In various embodiments, the epoxy silane resin has a degradation onsetof about 300° F. to about 800° F., about 300° F. to about 700° F., about450° F. to about 650° F., or about 300° F. or less, or about 320° F.,340, 360, 380, 400, 420, 440, 460, 480, 500, 550, 600, 650, 700, 750, orabout 800° F. or more.

In various embodiments, the epoxy silane resin has a peak degradationtemperature of about 550° F. to about 850° F., about 600° F. to about800° F., about 625° F. to about 765° F., or about 300° F. or less, orabout 320° F., 340, 360, 380, 400, 420, 440, 460, 480, 500, 550, 600,650, 700, 750, 800, 850, 900, or about 950° F. or more.

In some embodiments, the epoxy silane resin is substantiallyhomogeneous. In some embodiments the ratio of epoxy functional groups tosilane functional groups in the epoxy silane resin is about 1 to 1, 1 to1.1, 1 to 1.2, 1 to 1.3, 1 to 1.4, 1 to 1.6, 1 to 1.8, 1 to 2, 1 to 2.5,1 to 3, 1 to 4, 1 to 5, 1 to 6, 1 to 7, 1 to 8, 1 to 10, 1 to 15, 1 to20, 1 to 30, 1 to 40, 1 to 50, 1 to 60, 1 to 100, 1 to 200, 1 to 300, 1to 400, 1 to 500, 1 to 600, 1 to 700, 1 to 800, 1 to 900, or less thanabout 1 to 1000. In some embodiments the epoxy to silane ratio in theepoxy silane resin is about 1.1 to 1, 1.2 to 1, 1.3 to 1.4 to 1, 1.6 to1, 1.8 to 1, 2 to 1, 2.5 to 1, 3 to 1, 4 to 1, 5 to 1, 6 to 1, 7 to 1, 8to 1, 9 to 1, 10 to 1, 15 to 1, 20 to 1, 30 to 1, 40 to 1, 50 to 1, 60to 1, 70 to 1, 80 to 1, 90 to 1, 100 to 1, 200 to 1, 300 to 1, 400 to 1,500 to 1, 600 to 1, 700 to 1, 800 to 1, 900 to 1 or greater than about1000 to 1.

Epoxy Silane Monomer.

In various embodiments, the curable composition includes an epoxy silanemonomer. The epoxy silane monomer can form any suitable proportion ofthe curable composition, so long as the curable composition can be usedas described herein. For example, the epoxy silane monomer can be about40 wt. % to about 85 wt. %, about 50 wt. % to about 75 wt. %, about 55wt. % to about 70 wt. %, about 60 wt. % to about 65 wt. %, at least 5wt. %, or about 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70,75, 80, or about 85% wt. or more of the curable composition.

The term “epoxy silane monomer” as used herein refers to a molecule thatcontains both an epoxy functional group and a silane functional group.Non-limiting examples of epoxy silane monomers are Coatosil® MP200 andSilquest® A-187.

Coatosil® MP200 has the structure:

The variable f is about 2. The variable R^(A), at each occurrence, iseither —H or —CH₃ and the ratio of —H to —CH₃ is about 1 to 1.

Silquest® A-187 has the structure:

In some examples, the epoxy silane monomer can have the structure:

At each occurrence, R¹ and R² can each independently be chosen from —Hand substituted or unsubstituted (C₁-C₁₀)hydrocarbyl. The variable R³can be independently selected from —H, substituted or unsubstituted(C₁-C₁₀)hydrocarbyl, and the structure:

The variable R⁴ can be independently be chosen from —H and substitutedor unsubstituted (C₁-C₁₀)hydrocarbyl. At each occurrence, J can beindependently selected from a bond and a substituted or substituted(C₁-C₅)hydrocarbylene. At each occurrence, L can be independently chosenfrom substituted or unsubstituted (C₁-C₁₀)hydrocarbylene that can beinterrupted or terminated by 0, 1, 2, or 3 groups independently chosenfrom —O— and —S—. The variable c can be about 0 to about 10.

At each occurrence, R¹ and R² can each be independently chosen from —Hand substituted or unsubstituted (C₁-C₁₀)hydrocarbyl. At eachoccurrence, R¹ and R² can each independently be chosen from —H and(C₁-C₁₀)alkyl. At each occurrence, R¹ and R² can each independently bechosen from —H and (C₁-C₅)alkyl. At each occurrence, R¹ and R² can eachindependently be chosen from —H and methyl.

The variable R³ can be independently selected from —H, substituted orunsubstituted (C₁-C₁₀)hydrocarbyl, and the structure:

The variable R⁴ can independently be chosen from —H and substituted orunsubstituted (C₁-C₁₀)hydrocarbyl. At each occurrence, J can beindependently selected from a bond and a substituted or substituted(C₁-C₅)hydrocarbylene. At each occurrence, L can be independently chosenfrom a substituted or unsubstituted (C₁-C₁₀)hydrocarbylene that can beinterrupted or terminated by 0, 1, 2, or 3 groups independently chosenfrom —O— and —S—. The variable c can be about 0 to about 10.

The variable R⁴ can independently be chosen from —H and substituted orunsubstituted (C₁-C₁₀)hydrocarbyl. The variable R⁴ can independently bechosen from —H and (C₁-C₁₀)alkyl. The variable R⁴ can independently bechosen from —H and (C₁-C₅)alkyl. The variable R⁴ can independently bechosen from —H and methyl.

The variable J can independently be chosen from a bond and a substitutedor substituted (C₁-C₅)hydrocarbylene. The variable J can beindependently chosen from a bond and a (C₁-C₅)alkylene. The variable Jcan be propylene. The variable J can be a bond.

The variable L can independently be chosen from a substituted orunsubstituted (C₁-C₁₀)hydrocarbylene that can be interrupted orterminated by 0, 1, 2, or 3 groups independently chosen from —O— and—S—. The variable L can independently be chosen from a (C₁-C₅)alkylene,—OCH₂(CH₂)₃CH₂—, —OCH₂(CH₂)₂CH₂—, —OCH₂CH₂CH₂—, —OCH₂CH₂—, and —OCH₂—.The variable L can independently be chosen from —OCH₂(CH₂)₃CH₂—,—OCH₂(CH₂)2CH₂—, —OCH₂CH₂CH₂—, —OCH₂CH₂—, and —OCH₂—. The variable L, ateach occurrence, can be —OCH₂—.

The variable c can be about 0 to about 10, or about 0 to about 3, orabout 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, or about 10 or more.

In some examples R³ can be the structure

wherein at each occurrence, R² can be independently chosen from —H and(C₁-C₁₀)alkyl, R⁴ can be independently chosen from —H and (C₁-C₁₀)alkyl,at each occurrence, J can be independently chosen from a from a bond anda (C₁-C₅)alkylene, at each occurrence, L can be independently chosenfrom —OCH₂(CH₂)₃CH₂—, —OCH₂(CH₂)₂CH₂—, —OCH₂CH₂CH₂—, —OCH₂CH₂—, and—OCH₂—, and c can be about 0 to about 5.

In some examples R³ can be the structure

wherein at each occurrence, R² can be independently chosen from —H andmethyl, R⁴ can be independently chosen from —H and methyl, at eachoccurrence J can be —CH₂CH₂CH₂—, at each occurrence, L can be —OCH₂—,and c can be about 0 to about 3.

In some examples, the epoxy silane monomer can be a structure chosenfrom

The variable f can be about 0 to about 100, about 0 to about 90, about 0to about 80, about 0 to about 70, about 0 to about 60, about 0 to about50, about 0 to about 40, about 0 to about 30, about 0 to about 20, about0 to about 15 about 0 to 10, about 0 to about 8, about 0 to about 6,about 0 to about 4, about 0 to about 2 or about 0, 1, 2, 3, 4, 5, 6, 7,8, 9, 10, 15, 20, 30, 40, 50, 60, 70, 80, 90, or 100. The variableR^(A), at each occurrence, is independently chosen from —H and —CH₃. Theratio of —H to —CH₃ for the variable R^(A) can be about 1 to 3 to about3 to 1. The ratio of —H to —CH₃ for the variable R^(A) can be about 1 to100 to about 100 to 1, about 80 to 1 to about 1 to 80, about 1 to 60 toabout 60 to 1, about 1 to 40 to about 40 to 1, about 1 to 20 to about 20to 1, about 1 to 15 to about 15 to 1, about 1 to 10 to about 10 to 1,about 1 to 8 to about 8 to 1, about 1 to 6 to about 6 to 1, about 1 to 5to about 5 to 1, about 1 to 4 to about 4 to 1, about 1 to 3 to about 3to 1, about 1 to 2 to about 2 to 1, or about 1 to 1. In someembodiments, the variable R^(A), at each occurrence, is —H. In someembodiments, the variable R^(A), at each occurrence, is —CH₃.Hardener.

The curable composition includes a hardener. The hardener can form anysuitable proportion of the curable composition, so long as the curablecomposition can be used as described herein. For example, the hardenercan be about 5 wt. % to about 50 wt. %, about 10 wt. % to about 40 wt.%, about 15 wt. % to about 35 wt. %, about 17 wt. % to about 25 wt. %,at least 5 wt. %, or about 5, 10, 15, 20, 25, 30, 35, 40, 45, or about50 wt. % or more of the curable composition.

The term “hardener” as used herein refers a molecule capable ofcrosslinking epoxy silane monomers and/or epoxy monomers. In someembodiments, the crosslinking can result in polymerization and theformation of epoxy silane resins. Non-limiting examples of a hardenerinclude amine silane hardeners, Jeffamine D230, and Jeffamine ED-600.

Jeffamine® D230 has the structure

wherein the variable f has an average value of about 2.5.

Jeffamine® ED-600 has the structure

wherein y is about 9 and x+z has an average 3.6.

In some examples the hardener can be chosen from at least one primary orsecondary amine. The hardener can be any suitable hardener that canreact with the epoxy silane monomer to form an epoxy silane resin. Thehardener can be an epoxide-reactive hardener. The hardener can include anucleophilic group that can attack and open an epoxide, such as aprimary or secondary amine. The hardener can be an amine-functionalhardener, and can include at least one of an amine, an aromatic amine,an aliphatic amine, a cyclo-aliphatic amine, a polyamine, an amide, anda polyamide.

In some examples, the hardener can have the structure:

The variable R⁵, at each occurrence, can be independently chosen fromsubstituted or unsubstituted (C₁-C₁₀)hydrocarbylene. The variable A, ateach occurrence, can be independently chosen from —O— and —NH—. Thevariable L² can be independently chosen from substituted orunsubstituted (C₁-C₁₀)hydrocarbylene. The variable R⁶ can be chosen from—NH₂, —Si(OR⁷)₃, and —OH. The variable R⁷, at each occurrence, can bechosen from a (C₁-C₅)hydrocarbylene. The variable i can be about 1 toabout 80.

The variable R⁵, at each occurrence, can be independently chosen fromsubstituted or unsubstituted (C₁-C₁₀)hydrocarbylene. The variable R⁵, ateach occurrence, can be independently chosen from (C₁-C₅)alkylene. Thevariable R⁵, at each occurrence, can be independently chosen from—(CH₂)₂— and —CH(CH₃)CH₂—.

The variable A, at each occurrence, can be independently chosen from —O—and —NH—.

The variable L² can be chosen from substituted or unsubstituted(C₁-C₁₀)hydrocarbylene. The variable L² can be chosen from —CH₂CH(CH₃)—and —(CH₂)₃—.

The variable R⁶ can be chosen from chosen from —NH₂, —Si(OR⁷)₃, and —OH.The variable R⁷, at each occurrence, can be independently chosen from a(C₁-C₅)hydrocarbyl. The variable R⁶, at each occurrence, can beindependently be chosen from —Si(OR⁷)₃ and the variable R⁷ at eachoccurrence can be independently chosen from —CH₃, —CH₂CH₃, and—(CH₂)₂CH₃. The variable R⁶ can be —Si(OCH₃)₃.

The variable i can be about 1 to about 80, about 1 to about 70, about 1to about 60, about 1 to about 50, about 1 to about 40, about 1 to about30, about 1 to about 20, about 1 to about 10, about 1 to about 5, about2.5, or about 1, or 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15,16, 17, 18, 19, 20, 22, 24, 26, 28, 30, 35, 40, 45, 50, 55, 60, 65, 70,75, or 80 or more.

In some examples, the hardener can have a structure chosen from:

The variable n can be about 1 to about 80, about 65 to about 75, about28 to about 38, about 4 to about 8, or about 1 to about 3, or 1, 2, 3,4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 22, 24,26, 28, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, or 80 or more.

In some examples, the hardener can have the structure:

The variable y can be about 1 to about 45, about 1 to about 35, about 1to about 25, about 1 to about 15, or about 1 to about 10, or 1, 2, 3, 4,5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 22, 24, 26,28, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, or 80 or more. The variablesx and z, when added together, can be about 1 to about 10, or 1, 2, 3, 4,5, 6, 7, 8, 9, or 10 or more.Epoxy Monomer.

In various embodiments, the curable composition includes an epoxymonomer. The epoxy monomer can form any suitable proportion of thecurable composition, so long as the curable composition can be used asdescribed herein. For example, the epoxy silane monomer can be about 40wt. % to about 85 wt. %, about 50 wt. % to about 75 wt. %, about 55 wt.% to about 70 wt. %, about 60 wt. % to about 65 wt. %, at least 5 wt. %,or about 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80,or about 85% wt. or more of the curable composition.

In some examples, the epoxy monomer can be any monomer having one ormore epoxy functional groups. In some examples, the epoxy monomer can bean epoxide substituted (C₁-C₁₀)hydrocarbyl, wherein the(C₁-C₁₀)hydrocarbyl can be independently substituted or unsubstituted.In some examples, the epoxy monomer can be an epoxide substituted(C₁-C₁₀)hydrocarbylglycidyl ether, such as butyl glycidyl ether. In someexamples, the hardenable resin includes a combination of anepoxide-substituted (C₁-C₁₀)hydrocarbyl compound and apolyepoxide-substituted mono- or poly(C₅-C₂₀)aryl compound, such as acombination of butyl glycidyl ether and a diglycidyl ether of bisphenolA.

In some examples, the epoxy monomer can have a structure chosen from

The variable p can be about 1 to about 200, about 1 to about 150, about1 to about 100, about 1 to about 50, about 1 to about 25, about 1 to 15,about 1 to 10, or about 1 to 5, or 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11,12, 13, 14, 15, 16, 17, 18, 19, 20, 22, 24, 26, 28, 30, 35, 40, 45, 50,55, 60, 65, 70, 75, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180,190, 200 or more.Amine Silane Hardener

The curable composition includes an amine silane hardener. The aminesilane hardener can form any suitable proportion of the curablecomposition, so long as the curable composition can be used as describedherein. For example, the amine silane hardener can be about 5 wt. % toabout 50 wt. %, about 10 wt. % to about 40 wt. %, about 15 wt. % toabout 35 wt. %, about 17 wt. % to about 25 wt. %, at least 5 wt. %, orabout 5 wt. % or less, or about 10 wt. %, 15, 20, 25, 30, 35, 40, 45, orabout 50 wt. % or more of the curable composition.

The term “amine silane hardener” as used herein refers to a moleculethat contains both a primary amine and silane functional groups. Anon-limiting example of an amine silane hardener is Silquest® A-1120.

Silquest® A-1120 has the structure:

In some examples, the hardener can be chosen from a molecule thatcontains at least one primary or secondary amine and a silane. Thehardener can be an epoxide-reactive hardener. The amine silane hardenercan be an amine-functional hardener, and can include at least one of anamine, an aromatic amine, an aliphatic amine, a cyclo-aliphatic amine, apolyamine, an amide, and a polyamide.

In some examples, the amine silane hardener can have the structure:

The variable R⁸, at each occurrence, can be independently chosen fromsubstituted or unsubstituted (C₁-C₁₀)hydrocarbylene. The variable B, ateach occurrence, can be independently chosen from —O— and —NH—. Thevariable L³ can be independently chosen from substituted orunsubstituted (C₁-C₁₀)hydrocarbylene. The variable R⁹ can be —Si(OR¹⁰)₃.The variable R¹⁰, at each occurrence, can be chosen from a(C₁-C₅)hydrocarbyl. The variable q can be about 1 to about 80.

The variable R⁸, at each occurrence, can be independently chosen fromsubstituted or unsubstituted (C₁-C₁₀)hydrocarbylene. The variable R⁸, ateach occurrence, can be independently chosen from (C₁-C₅)alkylene. Thevariable R⁸ can be —(CH₂)₂.

The variable B, at each occurrence, can be independently chosen from—O—, and —NH—.

The variable L³ can be chosen from substituted or unsubstituted(C₁-C₁₀)hydrocarbylene. The variable L³ can be —(CH₂)₃—.

The variable R⁹ can be chosen from chosen from —NH₂, —Si(OR¹⁰)₃, and—OH. The variable R¹⁰, at each occurrence, can be independently chosenfrom a (C₁-C₅)hydrocarbylene. The variable R⁹, at each occurrence, canbe independently be chosen from —Si(OR¹⁰)₃ and the variable R¹⁰ at eachoccurrence can be independently chosen from —CH₃, —CH₂CH₃, and—(CH₂)₂CH₃. The variable R⁹ can be —Si(OCH₃)₃.

In some examples, the amine silane hardener can have the structure

Other Components.

The curable composition including the curable composition, or a mixtureincluding the curable composition, can include any suitable additionalcomponent in any suitable proportion, such that the curable composition,or mixture including the same, can be used as described herein.

In some embodiments, the curable composition or a cured product thereoffurther includes filler particles. The filler particles can includefillers, weighting agents, and combinations thereof. The fillerparticles can increase or decrease the density of the curablecomposition to achieve a proper density hierarchy for placement of thecurable composition and to account for the pore pressure and fracturepressure of the surrounding formation. The filler particles can bechosen to modify the mechanical properties of the cured product of thecurable composition or the fluid (rheological) properties of the liquid(uncured) curable composition. The filer particles can have the samedensity of curable composition so that the bulk density is not changed.The filler particle can include one of aluminum oxide, awaruite, bariumcarbonate, barium oxide, barite, calcium carbonate, calcium oxide,cenospheres, chromite, chromium oxide, copper, copper oxide, dolomite,galena, hematite, hollow glass microspheres, ilmenite, iron oxide,siderite, magnetite, magnesium oxide, manganese carbonate, manganesedioxide, manganese (IV) oxide, manganese oxide, manganese tetraoxide,manganese (II) oxide, manganese (III) oxide, molybdenum (IV) oxide,molybdenum oxide, molybdenum trioxide, Portland cement, pumice, pyrite,spherelite, silica, silver, tenorite, titania, titanium (II) oxide,titanium (III) oxide, titanium (IV) dioxide, zirconium oxide, zirconiumsilicate, zinc oxide, cement-kiln dust, unexpanded and expanded perlite,attapulgite, bentonite, zeolite, elastomers, sand, micronized polymers,waxes, polymer fibers, inorganic fibers and any combination thereof.

In some embodiments, the curable composition or a cured product thereoffurther includes a silane coupling agent. The silane coupling agent canbe any suitable silane coupling agent. For example, the silane couplingagent can be a (C₁-C₃₀)hydrocarbyl-substituted trimethoxysilane, whereinthe hydrocarbyl group is substituted or unsubstituted. The silanecoupling agent can be N-2-(aminoethyl)-3-aminopropyltrimethoxysilane,3-glycidoxypropyltrimethoxysilane, orn-beta-(aminoethyl)-gamma-aminopropyltrimethoxysilane. Any suitableamount of the curable composition or a cured product thereof can be thesilane coupling agent, such as about 0.001 wt. % to about 20 wt. %, orabout 0.001 wt. % to about 3 wt. %, or about 0.001 wt. % or less, orabout 0.01, 0.1, 1, 2, 3, 4, 5, 6, 8, 10, 12, 14, 16, 18, or about 20wt. % or more.

In some embodiments, the curable composition includes one or moreviscosifiers. The viscosifier can be any suitable viscosifier. Theviscosifier can affect the viscosity of the curable composition or asolvent that contacts the curable composition at any suitable time andlocation. In some embodiments, the viscosifier provides an increasedviscosity at least one of before injection into the subterraneanformation, at the time of injection into the subterranean formation,during travel through a tubular disposed in a borehole, once the curablecomposition reaches a particular subterranean location, or some periodof time after the curable composition reaches a particular subterraneanlocation. In some embodiments, the viscosifier can be about 0.000,1 wt.% to about 10 wt. % of the curable composition or a mixture includingthe same, about 0.004 wt. % to about 0.01 wt. %, or about 0.000,1 wt. %or less, 0.000,5 wt. %, 0.001, 0.005, 0.01, 0.05, 0.1, 0.5, 1, 2, 3, 4,5, 6, 7, 8, 9, or about 10 wt. % or more of the curable composition or amixture including the same.

The viscosifier can include at least one of a substituted orunsubstituted polysaccharide, and a substituted or unsubstitutedpolyalkene (e.g., a polyethylene, wherein the ethylene unit issubstituted or unsubstituted, derived from the corresponding substitutedor unsubstituted ethene), wherein the polysaccharide or polyalkene iscrosslinked or uncrosslinked. The viscosifier can include a polymerincluding at least one repeating unit derived from a monomer selectedfrom the group consisting of ethylene glycol, acrylamide, vinyl acetate,2-acrylamidomethylpropane sulfonic acid or its salts,trimethylammoniumethyl acrylate halide, and trimethylammoniumethylmethacrylate halide. The viscosifier can include a crosslinked gel or acrosslinkable gel. The viscosifier can include at least one of a linearpolysaccharide, and a poly((C₂-C₁₀)alkene), wherein the (C₂-C₁₀)alkeneis substituted or unsubstituted. The viscosifier can include at leastone of poly(acrylic acid) or (C₁-C₅)alkyl esters thereof,poly(methacrylic acid) or (C₁-C₅)alkyl esters thereof, poly(vinylacetate), poly(vinyl alcohol), poly(ethylene glycol), poly(vinylpyrrolidone), polyacrylamide, poly (hydroxyethyl methacrylate),alginate, chitosan, curdlan, dextran, derivatized dextran, emulsan, agalactoglucopolysaccharide, gellan, glucuronan, N-acetyl-glucosamine,N-acetyl-heparosan, hyaluronic acid, kefiran, lentinan, levan, mauran,pullulan, scleroglucan, schizophyllan, stewartan, succinoglycan,xanthan, diutan, welan, starch, derivatized starch, tamarind,tragacanth, guar gum, derivatized guar gum (e.g., hydroxypropyl guar,carboxy methyl guar, or carboxymethyl hydroxypropyl guar), gum ghatti,gum arabic, locust bean gum, cellulose, and derivatized cellulose (e.g.,carboxymethyl cellulose, hydroxyethyl cellulose, carboxymethylhydroxyethyl cellulose, hydroxypropyl cellulose, or methyl hydroxy ethylcellulose).

In some embodiments, the viscosifier can include at least one of apoly(vinyl alcohol) homopolymer, poly(vinyl alcohol) copolymer, acrosslinked poly(vinyl alcohol) homopolymer, and a crosslinkedpoly(vinyl alcohol) copolymer. The viscosifier can include a poly(vinylalcohol) copolymer or a crosslinked poly(vinyl alcohol) copolymerincluding at least one of a graft, linear, branched, block, and randomcopolymer of vinyl alcohol and at least one of a substituted orunsubstituted (C₂-C₅₀)hydrocarbyl having at least one aliphaticunsaturated C—C bond therein, and a substituted or unsubstituted(C₂-C₅₀)alkene. The viscosifier can include a poly(vinyl alcohol)copolymer or a crosslinked poly(vinyl alcohol) copolymer including atleast one of a graft, linear, branched, block, and random copolymer ofvinyl alcohol and at least one of vinyl phosphonic acid, vinylidenediphosphonic acid, substituted or unsubstituted2-acrylamido-2-methylpropanesulfonic acid, a substituted orunsubstituted (C₁-C₂₀)alkenoic acid, propenoic acid, butenoic acid,pentenoic acid, hexenoic acid, octenoic acid, nonenoic acid, decenoicacid, acrylic acid, methacrylic acid, hydroxypropyl acrylic acid,acrylamide, fumaric acid, methacrylic acid, hydroxypropyl acrylic acid,vinyl phosphonic acid, vinylidene diphosphonic acid, itaconic acid,crotonic acid, mesoconic acid, citraconic acid, styrene sulfonic acid,allyl sulfonic acid, methallyl sulfonic acid, vinyl sulfonic acid, and asubstituted or unsubstituted (C₁-C₂₀)alkyl ester thereof. Theviscosifier can include a poly(vinyl alcohol) copolymer or a crosslinkedpoly(vinyl alcohol) copolymer including at least one of a graft, linear,branched, block, and random copolymer of vinyl alcohol and at least oneof vinyl acetate, vinyl propanoate, vinyl butanoate, vinyl pentanoate,vinyl hexanoate, vinyl 2-methyl butanoate, vinyl 3-ethylpentanoate, andvinyl 3-ethylhexanoate, maleic anhydride, a substituted or unsubstituted(C₁-C₂₀)alkenoic substituted or unsubstituted (C₁-C₂₀)alkanoicanhydride, a substituted or unsubstituted (C₁-C₂₀)alkenoic substitutedor unsubstituted (C₁-C₂₀)alkenoic anhydride, propenoic acid anhydride,butenoic acid anhydride, pentenoic acid anhydride, hexenoic acidanhydride, octenoic acid anhydride, nonenoic acid anhydride, decenoicacid anhydride, acrylic acid anhydride, fumaric acid anhydride,methacrylic acid anhydride, hydroxypropyl acrylic acid anhydride, vinylphosphonic acid anhydride, vinylidene diphosphonic acid anhydride,itaconic acid anhydride, crotonic acid anhydride, mesoconic acidanhydride, citraconic acid anhydride, styrene sulfonic acid anhydride,allyl sulfonic acid anhydride, methallyl sulfonic acid anhydride, vinylsulfonic acid anhydride, and an N—(C₁-C₁₀)alkenyl nitrogen containingsubstituted or unsubstituted (C₁-C₁₀)heterocycle. The viscosifier caninclude a poly(vinyl alcohol) copolymer or a crosslinked poly(vinylalcohol) copolymer including at least one of a graft, linear, branched,block, and random copolymer that includes apoly(vinylalcohol/acrylamide) copolymer, apoly(vinylalcohol/2-acrylamido-2-methylpropanesulfonic acid) copolymer,a poly (acrylamide/2-acrylamido-2-methylpropanesulfonic acid) copolymer,or a poly(vinylalcohol/N-vinylpyrrolidone) copolymer.

The viscosifier can include a crosslinked poly(vinyl alcohol)homopolymer or copolymer including a crosslinker including at least oneof chromium, aluminum, antimony, zirconium, titanium, calcium, boron,iron, silicon, copper, zinc, magnesium, and an ion thereof. Theviscosifier can include a crosslinked poly(vinyl alcohol) homopolymer orcopolymer including a crosslinker including at least one of an aldehyde,an aldehyde-forming compound, a carboxylic acid or an ester thereof, asulfonic acid or an ester thereof, a phosphonic acid or an esterthereof, an acid anhydride, and an epihalohydrin.

In various embodiments, the curable composition can include one or morecrosslinkers. The crosslinker can be any suitable crosslinker. In someexamples, the crosslinker can be incorporated in a crosslinkedviscosifier, and in other examples, the crosslinker can crosslink acrosslinkable material (e.g., downhole). The crosslinker can include atleast one of chromium, aluminum, antimony, zirconium, titanium, calcium,boron, iron, silicon, copper, zinc, magnesium, and an ion thereof. Thecrosslinker can include at least one of boric acid, borax, a borate, a(C₁-C₃₀)hydrocarbylboronic acid, a (C₁-C₃₀)hydrocarbyl ester of a(C₁-C₃₀)hydrocarbylboronic acid, a (C₁-C₃₀)hydrocarbylboronicacid-modified polyacrylamide, ferric chloride, disodium octaboratetetrahydrate, sodium metaborate, sodium diborate, sodium tetraborate,disodium tetraborate, a pentaborate, ulexite, colemanite, magnesiumoxide, zirconium lactate, zirconium triethanol amine, zirconium lactatetriethanolamine, zirconium carbonate, zirconium acetylacetonate,zirconium malate, zirconium citrate, zirconium diisopropylamine lactate,zirconium glycolate, zirconium triethanol amine glycolate, zirconiumlactate glycolate, titanium lactate, titanium malate, titanium citrate,titanium ammonium lactate, titanium triethanolamine, titaniumacetylacetonate, aluminum lactate, and aluminum citrate. In someembodiments, the crosslinker can be a (C₁-C₂₀)alkylenebiacrylamide(e.g., methylenebisacrylamide), a poly((C₁-C₂₀)alkenyl)-substitutedmono- or poly-(C₁-C₂₀)alkyl ether (e.g., pentaerythritol allyl ether),and a poly(C₂-C₂₀)alkenylbenzene (e.g., divinylbenzene). In someembodiments, the crosslinker can be at least one of alkyl diacrylate,ethylene glycol diacrylate, ethylene glycol dimethacrylate, polyethyleneglycol diacrylate, polyethylene glycol dimethacrylate, ethoxylatedbisphenol A diacrylate, ethoxylated bisphenol A dimethacrylate,ethoxylated trimethylol propane triacrylate, ethoxylated trimethylolpropane trimethacrylate, ethoxylated glyceryl triacrylate, ethoxylatedglyceryl trimethacrylate, ethoxylated pentaerythritol tetraacrylate,ethoxylated pentaerythritol tetramethacrylate, ethoxylateddipentaerythritol hexaacrylate, polyglyceryl monoethylene oxidepolyacrylate, polyglyceryl polyethylene glycol polyacrylate,dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate,neopentyl glycol diacrylate, neopentyl glycol dimethacrylate,pentaerythritol triacrylate, pentaerythritol trimethacrylate,trimethylol propane triacrylate, trimethylol propane trimethacrylate,tricyclodecane dimethanol diacrylate, tricyclodecane dimethanoldimethacrylate, 1,6-hexanediol diacrylate, and 1,6-hexanedioldimethacrylate. The crosslinker can be about 0.000,01 wt. % to about 5wt. % of the curable composition or a mixture including the same, about0.001 wt. % to about 0.01 wt. %, or about 0.000,01 wt. % or less, orabout 0.000,05 wt. %, 0.000,1, 0.000,5, 0.001, 0.005, 0.01, 0.05, 0.1,0.5, 1, 2, 3, 4, or about 5 wt. % or more.

In some embodiments, the curable composition can include one or morebreakers. The breaker can be any suitable breaker, such that thesurrounding fluid (e.g., a fracturing fluid) can be at least partiallybroken for more complete and more efficient recovery thereof, such as atthe conclusion of the hydraulic fracturing treatment. In someembodiments, the breaker can be encapsulated or otherwise formulated togive a delayed-release or a time-release of the breaker, such that thesurrounding liquid can remain viscous for a suitable amount of timeprior to breaking. The breaker can be any suitable breaker; for example,the breaker can be a compound that includes a Na⁺, K⁺, Li⁺, Zn⁺, NH₄ ⁺,Fe²⁺, Fe³⁺, Cu¹⁺, Ca²⁺, Ca²⁺, Mg²⁺, Zn²⁺, and an Al³⁺ salt of achloride, fluoride, bromide, phosphate, or sulfate ion. In someexamples, the breaker can be an oxidative breaker or an enzymaticbreaker. An oxidative breaker can be at least one of a Na⁺, K⁺, Li⁺,Zn⁺, NH₄ ⁺, Fe²⁺, Fe³⁺, Cu¹⁺, Cu²⁺, Ca²⁺, Mg²⁺, Zn²⁺, and an Al³⁺ saltof a persulfate, percarbonate, perborate, peroxide, perphosphosphate,permanganate, chlorite, or hyporchlorite ion. An enzymatic breaker canbe at least one of an alpha or beta amylase, amyloglucosidase,oligoglucosidase, invertase, maltase, cellulase, hemi-cellulase, andmannanohydrolase. The breaker can be about 0.001 wt. % to about 30 wt. %of the curable composition or a mixture including the same, or about0.01 wt. % to about 5 wt. %, or about 0.001 wt. % or less, or about0.005 wt. %, 0.01, 0.05, 0.1, 0.5, 1, 2, 3, 4, 5, 6, 8, 10, 12, 14, 16,18, 20, 22, 24, 26, 28, or about 30 wt. % or more.

The curable composition, or a mixture including the curable composition,can include any suitable fluid. For example, the fluid can be at leastone of crude oil, dipropylene glycol methyl ether, dipropylene glycoldimethyl ether, dipropylene glycol methyl ether, dipropylene glycoldimethyl ether, dimethyl formamide, diethylene glycol methyl ether,ethylene glycol butyl ether, diethylene glycol butyl ether,butylglycidyl ether, propylene carbonate, D-limonene, a C₂-C₄₀ fattyacid C₁-C₁₀ alkyl ester (e.g., a fatty acid methyl ester),tetrahydrofurfuryl methacrylate, tetrahydrofurfuryl acrylate, 2-butoxyethanol, butyl acetate, butyl lactate, furfuryl acetate, dimethylsulfoxide, dimethyl formamide, a petroleum distillation product offraction (e.g., diesel, kerosene, napthas, and the like) mineral oil, ahydrocarbon oil, a hydrocarbon including an aromatic carbon-carbon bond(e.g., benzene, toluene), a hydrocarbon including an alpha olefin,xylenes, an ionic liquid, methyl ethyl ketone, an ester of oxalic,maleic or succinic acid, methanol, ethanol, propanol (iso- or normal-),butyl alcohol (iso-, tert-, or normal-), an aliphatic hydrocarbon (e.g.,cyclohexanone, hexane), water, brine, produced water, flowback water,brackish water, and sea water. The fluid can form about 0.001 wt. % toabout 99.999 wt. % of the curable composition, or a mixture includingthe same, or about 0.001 wt. % or less, 0.01 wt. %, 0.1, 1, 2, 3, 4, 5,6, 8, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85,90, 95, 96, 97, 98, 99, 99.9, 99.99, or about 99.999 wt. % or more.

The curable composition including the curable composition or a mixtureincluding the same can include any suitable downhole fluid. The curablecomposition can be combined with any suitable downhole fluid before,during, or after the placement of the curable composition in thesubterranean formation or the contacting of the curable composition andthe subterranean material. In some examples, the curable composition iscombined with a downhole fluid above the surface, and then the combinedcomposition is placed in a subterranean formation or contacted with asubterranean material. In another example, the curable composition isinjected into a subterranean formation to combine with a downhole fluid,and the combined composition is contacted with a subterranean materialor is considered to be placed in the subterranean formation. Theplacement of the curable composition in the subterranean formation caninclude contacting the subterranean material and the mixture. Anysuitable weight percent of the curable composition or of a mixtureincluding the same that is placed in the subterranean formation orcontacted with the subterranean material can be the downhole fluid, suchas about 0.001 wt. % to about 99.999 wt. %, about 0.01 wt. % to about99.99 wt. %, about 0.1 wt. % to about 99.9 wt. %, about 20 wt. % toabout 90 wt. %, or about 0.001 wt. % or less, or about 0.01 wt. %, 0.1,1, 2, 3, 4, 5, 10, 15, 20, 30, 40, 50, 60, 70, 80, 85, 90, 91, 92, 93,94, 95, 96, 97, 98, 99, 99.9, 99.99 wt. %, or about 99.999 wt. % or moreof the curable composition or mixture including the same.

In some embodiments, the curable composition, or a mixture including thesame, can include any suitable amount of any suitable material used in adownhole fluid. For example, the curable composition or a mixtureincluding the same can include water, saline, aqueous base, acid, oil,organic solvent, synthetic fluid oil phase, aqueous solution, alcohol orpolyol, cellulose, starch, alkalinity control agents, acidity controlagents, density control agents, density modifiers, emulsifiers,dispersants, polymeric stabilizers, crosslinking agents, polyacrylamide,a polymer or combination of polymers, antioxidants, heat stabilizers,foam control agents, solvents, diluents, plasticizer, filler orinorganic particle, pigment, dye, precipitating agent, rheologymodifier, oil-wetting agents, set retarding additives, surfactants,gases, weight reducing additives, heavy-weight additives, lostcirculation materials, filtration control additives, salts (e.g., anysuitable salt, such as potassium salts such as potassium chloride,potassium bromide, potassium formate; calcium salts such as calciumchloride, calcium bromide, calcium formate; cesium salts such as cesiumchloride, cesium bromide, cesium formate, or a combination thereof),fibers, thixotropic additives, breakers, crosslinkers, rheologymodifiers, curing accelerators, curing retarders, pH modifiers,chelating agents, scale inhibitors, enzymes, resins, water controlmaterials, oxidizers, markers, Portland cement, pozzolana cement, gypsumcement, high alumina content cement, slag cement, silica cement, flyash, metakaolin, shale, zeolite, a crystalline silica compound,amorphous silica, hydratable clays, microspheres, lime, or a combinationthereof. In various embodiments, the curable composition or a mixtureincluding the same can include one or more additive components such as:COLDTROL®, ATC®, OMC 2™, and OMC 42™ thinner additives; RHEMOD™viscosifier and suspension agent; TEMPERUS™ and VIS-PLUS® additives forproviding temporary increased viscosity; TAU-MOD™viscosifying/suspension agent; ADAPTA®, DURATONE® HT, THERMO TONE™,BDF™-366, and BDF™-454 filtration control agents; LIQUITONE™ polymericfiltration agent and viscosifier; FACTANT™ emulsion stabilizer; LESUPERMUL™, EZ MUL® NT, and FORTI-MUL® emulsifiers; DRIL TREAT® oilwetting agent for heavy fluids; BARACARB® bridging agent; BAROID®weighting agent; BAROLIFT® hole sweeping agent; SWEEP-WATE® sweepweighting agent; BDF-508 rheology modifier; and GELTONE® II organophilicclay. In various embodiments, the curable composition or a mixtureincluding the same can include one or more additive components such as:X-TEND® II, PAC™-R, PAC™-L, LIQUI-VIS® EP, BRINEDRIL-VIS™, BARAZAN®,N-VIS®, and AQUAGEL® viscosifiers; THERMA-CHEK®, N-DRIL™, N-DRIL™ HTPLUS, IMPERMEX®, FILTERCHEK™, DEXTRID®, CARBONOX®, and BARANEX® Rfiltration control agents; PERFORMATROL®, GEM™, EZ-MUD®, CLAY GRABBER®,CLAYSEAL®, CRYSTAL-DRIL®, and CLAY SYNC™ II shale stabilizers;NXS-LUBE™, EP MUDLUBE®, and DRIL-N-SLIDE™ lubricants; QUIK-THIN®,IRON-THIN™, and ENVIRO-THIN™ thinners; SOURSCAV™ scavenger; BARACOR®corrosion inhibitor; and WALL-NUT®, SWEEP-WATE®, STOPPIT™, PLUG-GIT®,BARACARB®, DUO-SQUEEZE®, BAROFIBRE™, STEELSEAL®, and HYDRO-PLUG® lostcirculation management materials. Any suitable proportion of the curablecomposition or mixture including the curable composition can include anyoptional component listed in this paragraph, such as about 0.001 wt. %to about 99.999 wt. %, about 0.01 wt. % to about 99.99 wt. %, about 0.1wt. % to about 99.9 wt. %, about 20 to about 90 wt. %, or about 0.001wt. % or less, or about 0.01 wt. %, 0.1, 1, 2, 3, 4, 5, 10, 15, 20, 30,40, 50, 60, 70, 80, 85, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.9,99.99 wt. %, or about 99.999 wt. % or more of the curable composition ormixture.

In various embodiments, the curable composition or mixture can include aproppant, an epoxy silane resin-coated proppant, resin-coated proppant,an encapsulated epoxy silane resin, or a combination thereof. A proppantis a material that keeps an induced hydraulic fracture at leastpartially open during or after a fracturing treatment. Proppants can betransported into the subterranean formation (e.g., downhole) to thefracture using fluid, such as fracturing fluid or another fluid. Ahigher-viscosity fluid can more effectively transport proppants to adesired location in a fracture, especially larger proppants, by moreeffectively keeping proppants in a suspended state within the fluid.Examples of proppants can include sand, gravel, glass beads, polymerbeads, ground products from shells and seeds such as walnut hulls, andmanmade materials such as ceramic proppant, bauxite, tetrafluoroethylenematerials (e.g., TEFLON™ polytetrafluoroethylene), fruit pit materials,processed wood, composite particulates prepared from a binder and finegrade particulates such as silica, alumina, fumed silica, carbon black,graphite, mica, titanium dioxide, meta-silicate, calcium silicate,kaolin, talc, zirconia, boron, fly ash, hollow glass microspheres, andsolid glass, or mixtures thereof. In some embodiments, the proppant canhave an average particle size, wherein particle size is the largestdimension of a particle, of about 0.001 mm to about 3 mm, about 0.15 mmto about 2.5 mm, about 0.25 mm to about 0.43 mm, about 0.43 mm to about0.85 mm, about 0.85 mm to about 1.18 mm, about 1.18 mm to about 1.70 mm,or about 1.70 to about 2.36 mm. In some embodiments, the proppant canhave a distribution of particle sizes clustering around multipleaverages, such as one, two, three, or four different average particlesizes. The curable composition or mixture can include any suitableamount of proppant, such as about 0.01 wt. % to about 99.99 wt. %, about0.1 wt. % to about 80 wt. %, about 10 wt. % to about 60 wt. %, or about0.01 wt. % or less, or about 0.1 wt. %, 1, 2, 3, 4, 5, 10, 15, 20, 30,40, 50, 60, 70, 80, 85, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, about99.9 wt. %, or about 99.99 wt. % or more.

System or Apparatus.

In various embodiments, the present invention provides a system. Thesystem can be any suitable system that can use or that can be generatedby use of an embodiment of the curable composition described herein in asubterranean formation, or that can perform or be generated byperformance of a method for using the curable composition describedherein. The system can include a composition including an embodiment ofthe curable composition described herein. In some embodiments the systemcan include an epoxy silane resin cured reaction product formed from anembodiment of the curable composition described herein. The system canalso include a subterranean formation including the curable compositiontherein. In some embodiments, the curable composition in the system canalso include a downhole fluid, or the system can include a mixture ofthe curable composition and downhole fluid. In some embodiments, thesystem can include a tubular, and a pump configured to pump the curablecomposition into the subterranean formation through the tubular.

Various embodiments provide systems and apparatus configured fordelivering the curable composition described herein to a subterraneanlocation and for using the curable composition therein, such as for afracturing operation (e.g., pre-pad, pad, slurry, or finishing stages).In various embodiments, the system or apparatus can include a pumpfluidly coupled to a tubular (e.g., any suitable type of oilfield pipe,such as pipeline, drill pipe, production tubing, and the like), with thetubular containing a composition including the curable compositiondescribed herein or a reaction product thereof (e.g., an epoxy silanecured reaction product thereof).

The pump can be a high pressure pump in some embodiments. As usedherein, the term “high pressure pump” will refer to a pump that iscapable of delivering a fluid to a subterranean formation (e.g.,downhole) at a pressure of about 1000 psi or greater. A high pressurepump can be used when it is desired to introduce the curable compositionto a subterranean formation at or above a fracture gradient of thesubterranean formation, but it can also be used in cases wherefracturing is not desired. In some embodiments, the high pressure pumpcan be capable of fluidly conveying particulate matter, such as proppantparticulates, into the subterranean formation. Suitable high pressurepumps will be known to one having ordinary skill in the art and caninclude floating piston pumps and positive displacement pumps.

In other embodiments, the pump can be a low pressure pump. As usedherein, the term “low pressure pump” will refer to a pump that operatesat a pressure of about 1000 psi or less. In some embodiments, a lowpressure pump can be fluidly coupled to a high pressure pump that isfluidly coupled to the tubular. That is, in such embodiments, the lowpressure pump can be configured to convey the curable composition to thehigh pressure pump. In such embodiments, the low pressure pump can “stepup” the pressure of the curable composition before it reaches the highpressure pump.

In some embodiments, the systems or apparatuses described herein canfurther include a mixing tank that is upstream of the pump and in whichthe curable composition is formulated. In various embodiments, the pump(e.g., a low pressure pump, a high pressure pump, or a combinationthereof) can convey the curable composition from the mixing tank orother source of the curable composition to the tubular. In otherembodiments, however, the curable composition can be formulated offsiteand transported to a worksite, in which case the curable composition canbe introduced to the tubular via the pump directly from its shippingcontainer (e.g., a truck, a railcar, a barge, or the like) or from atransport pipeline. In either case, the curable composition can be drawninto the pump, elevated to an appropriate pressure, and then introducedinto the tubular for delivery to the subterranean formation.

FIG. 1 shows an illustrative schematic of systems and apparatuses thatcan deliver embodiments of the curable compositions of the presentinvention to a subterranean location, according to one or moreembodiments. It should be noted that while FIG. 1 generally depicts aland-based system or apparatus, it is to be recognized that like systemsand apparatuses can be operated in subsea locations as well. Embodimentsof the present invention can have a different scale than that depictedin FIG. 1. As depicted in FIG. 1, system or apparatus 1 can includemixing tank 10, in which an embodiment of the curable composition can beformulated. The curable composition can be conveyed via line 12 towellhead 14, where the curable composition enters tubular 16, withtubular 16 extending from wellhead 14 into subterranean formation 18.Upon being ejected from tubular 16, the curable composition cansubsequently penetrate into subterranean formation 18. Pump 20 can beconfigured to raise the pressure of the curable composition to a desireddegree before its introduction into tubular 16. It is to be recognizedthat system or apparatus 1 is merely exemplary in nature and variousadditional components can be present that have not necessarily beendepicted in FIG. 1 in the interest of clarity. In some examples,additional components that can be present include supply hoppers,valves, condensers, adapters, joints, gauges, sensors, compressors,pressure controllers, pressure sensors, flow rate controllers, flow ratesensors, temperature sensors, and the like.

Although not depicted in FIG. 1, at least part of the curablecomposition can, in some embodiments, flow back to wellhead 14 and exitsubterranean formation 18. The curable composition that flows back canbe substantially diminished in the concentration of one or morecomponents of the curable composition originally placed in thesubterranean composition. In some embodiments, the curable compositionthat has flowed back to wellhead 14 can subsequently be recovered, andin some examples reformulated, and recirculated to subterraneanformation 18.

It is also to be recognized that the disclosed composition can alsodirectly or indirectly affect the various downhole or subterraneanequipment and tools that can come into contact with the curablecomposition during operation. Such equipment and tools can includewellbore casing, wellbore liner, completion string, insert strings,drill string, coiled tubing, slickline, wireline, drill pipe, drillcollars, mud motors, downhole motors and/or pumps, surface-mountedmotors and/or pumps, centralizers, turbolizers, scratchers, floats(e.g., shoes, collars, valves, and the like), logging tools and relatedtelemetry equipment, actuators (e.g., electromechanical devices,hydromechanical devices, and the like), sliding sleeves, productionsleeves, plugs, screens, filters, flow control devices (e.g., inflowcontrol devices, autonomous inflow control devices, outflow controldevices, and the like), couplings (e.g., electro-hydraulic wet connect,dry connect, inductive coupler, and the like), control lines (e.g.,electrical, fiber optic, hydraulic, and the like), surveillance lines,drill bits and reamers, sensors or distributed sensors, downhole heatexchangers, valves and corresponding actuation devices, tool seals,packers, cement plugs, bridge plugs, and other wellbore isolationdevices or components, and the like. Any of these components can beincluded in the systems and apparatuses generally described above anddepicted in FIG. 1.

Composition for Treatment of a Subterranean Formation.

Various embodiments provide a composition for treatment of asubterranean formation. The curable composition can be any suitablecomposition that can be used to perform an embodiment of the method fortreatment of a subterranean formation described herein.

For example, the curable composition can include an epoxy silanemonomer, a hardener, and a carrier fluid, as described herein. Forexample, the curable composition can include an epoxy monomer, an aminesilane hardener, and a carrier fluid, as described herein

Method for Preparing a Composition for Treatment of a SubterraneanFormation.

In various embodiments, the present invention provides a method forpreparing a composition for treatment of a subterranean formation. Themethod can be any suitable method that produces an embodiment of thecurable composition described herein.

For example, the method can include forming a curable compositionincluding an epoxy silane monomer, a hardener, and a carrier fluid, asdescribed herein. For example, the method can include forming a curablecomposition including an epoxy monomer, an amine silane hardener, and acarrier fluid, as described herein.

EXAMPLES

Various embodiments of the present invention can be better understood byreference to the following Examples which are offered by way ofillustration. The present invention is not limited to the Examples givenherein.

Example 1. Preparation of Epoxy Silane Resins

Preparation of epoxy silane resins: The silane containing monomer wasmixed with water for 60 minutes. The hardener was then added and stirredto produce a homogeneous solution. The samples were placed in molds andcured overnight at room temperature and then at 122° F. for anadditional 24 hours. The resin cylinders were removed from their moldscured an additional 24 hours at 150° F. The epoxy silane resins preparedare samples 1-4 in Table 1.

Example 2. Preparation of Epoxy Resin Samples

The resin and hardener were stirred together for 60 minutes at roomtemperature. The samples were poured in molds and cured at roomtemperature overnight. The samples were cured for an additional 24 hoursat 122° F. The resin cylinders were removed from their molds and curedan additional 24 hours at 150° F. The epoxy resins prepared forcomparative testing are samples 4-7 in Table 1.

TABLE 1 Epoxy Silane Resins and Epoxy Resins. Sam- Epoxy Hardener Waterple Epoxy (g) Hardener (g) (g) 1 Coatosil ® MP200 10 Jeffamine ® 3.4 0.9D230 2 Silquest ® A-187 10 Jeffamine ® 2.7 2.8 D230 3 Cyclohexanedi- 10Silquest ® 5.8 1.4 methanol A-1120 diglycidyl ether 4 Silquest ® A-18710 Silquest ® 3.2 4.0 A-1120 5 Cyclohexanedi- 20 Jeffamine ® 9.0 —methanol D230 diglycidyl ether 6 Polyethyleneglycol 20 Jeffamine ® 4.6 —diglycidyl ether D230 7 Trimethylolpropane 20 Jeffamine ® 11.4 —triglycidyl ether D230

Example 3. Thermal Gravimetric Analysis (TGA)

The resin formulations shown in Table 1 were tested for thermalstability by TGA. TGA was performed as follows: A small piece of resinsample was placed in a platinum pan and placed in the TGA instrument.Under a nitrogen atmosphere, the temperature was increased from roomtemperature to 1000° C. at 10° C. per minute. The sample was held at1000° C. for 2.5 minutes. The weight of the sample was continuouslyrecorded throughout the experiment. The first derivative of the sampleweight was calculated and the peak of the first derivative was taken asthe peak degradation temperature (e.g., the temperature at whichdegradation weight loss is highest). The departure of the weight fromits baseline is taken as the degradation onset. The difference betweenthe initial sample weight and final sample weight is the total masslost.

The results of the TGA are shown in Table 2. Example thermograms areillustrated in FIG. 2 and FIG. 3. FIG. 2 illustrates a thermogram ofSample 2. FIG. 3 illustrates a thermogram of Sample 5. In all cases thepeak degradation temperature of the epoxy silane resins was higher thanfor all of the epoxy resins. Further, in 3 out of 4 epoxy silane resins,the onset of degradation came at higher temperatures than for the epoxyresins. Finally, the total mass loss in the epoxy silane resins was lessthan that of the epoxy resins. These results show that epoxy silaneresins are stable at higher temperatures than traditional epoxy resins.These resins are low viscosity and can be mixed in the same manner asepoxy resins. As such, epoxy silane resins can be employed in wells withBHS temperatures higher than those serviced with epoxy resins.

TABLE 2 TGA results. Degradation Peak Degredation Total Mass SampleResin Type Onset (° F.) Temp. (° F.) Loss (%) 1 Epoxy silane 628 73466.8 2 Epoxy silane 646 752 65.7 3 Epoxy silane 509 635 78.7 4 Epoxysilane 601 761 55.2 5 Epoxy 493 563 97.9 6 Epoxy 516 554 98.7 7 Epoxy477 626 97.7

The terms and expressions that have been employed are used as terms ofdescription and not of limitation, and there is no intention in the useof such terms and expressions of excluding any equivalents of thefeatures shown and described or portions thereof, but it is recognizedthat various modifications are possible within the scope of theembodiments of the present invention. Thus, it should be understood thatalthough the present invention has been specifically disclosed byspecific embodiments and optional features, modification and variationof the concepts herein disclosed may be resorted to by those of ordinaryskill in the art, and that such modifications and variations areconsidered to be within the scope of embodiments of the presentinvention.

Additional Embodiments

The following exemplary embodiments are provided, the numbering of whichis not to be construed as designating levels of importance:

Embodiment 1 provides a method of treating a subterranean formation, themethod comprising:

placing in a subterranean formation a curable composition comprising

-   -   an epoxy silane monomer;    -   a hardener; and    -   a carrier fluid; and    -   curing the curable composition to form an epoxy silane resin.

Embodiment 2 provides the method of Embodiment 1, wherein the curablecomposition is a composition for at least one of remediating,consolidating, cementing, and plugging for abandonment a subterraneanformation.

Embodiment 3 provides the method of any one of Embodiments 1-2, whereinthe carrier fluid comprises water.

Embodiment 4 provides the method of any one of Embodiments 1-3, whereinabout 1 wt. % to about 40 wt. % of the curable composition is thecarrier fluid.

Embodiment 5 provides the method of any one of Embodiments 1-4, whereinabout 5 wt. % to about 25 wt. % of the curable composition is thecarrier fluid.

Embodiment 6 provides the method of any one of Embodiments 1-5, whereinthe method further comprises obtaining or providing the curablecomposition, wherein the obtaining or providing of the curablecomposition occurs above-surface.

Embodiment 7 provides the method of any one of Embodiments 1-6, whereinthe method further comprises obtaining or providing the curablecomposition, wherein the obtaining or providing of the curablecomposition occurs in the subterranean formation.

Embodiment 8 provides the method of any one of Embodiments 1-7, whereinthe curing occurs at least partially above-surface.

Embodiment 9 provides the method of any one of Embodiments 1-8, whereinthe curing occurs at least partially in the subterranean formation.

Embodiment 10 provides the method of any one of Embodiments 1-9, whereinthe epoxy silane resin has a degradation onset of about 300° F. to about700° F.

Embodiment 11 provides the method of any one of Embodiments 1-10,wherein the epoxy silane resin has a degradation onset of about 300° F.to about 800° F.

Embodiment 12 provides the method of any one of Embodiments 1-11,wherein the epoxy silane resin has a degradation onset of about 450° F.to about 650° F.

Embodiment 13 provides the method of any one of Embodiments 1-12,wherein the epoxy silane resin has a peak degradation temperature ofabout 550° F. to about 850° F.

Embodiment 14 provides the method of any one of Embodiments 1-13,wherein the epoxy silane resin has a peak degradation temperature ofabout 625° F. to about 765° F.

Embodiment 15 provides the method of any one of Embodiments 1-14,wherein the epoxy silane resin is substantially homogeneous.

Embodiment 16 provides the method of any one of Embodiments 1-15,wherein about 40 wt. % to about 85 wt. % of the curable composition isthe epoxy silane monomer.

Embodiment 17 provides the method of any one of Embodiments 1-16,wherein about 50 wt. % to about 75 wt. % of the curable composition isthe epoxy silane monomer.

Embodiment 18 provides the method of any one of Embodiments 1-17,wherein 55 wt. % to about 70 wt. % of the curable composition is theepoxy silane monomer.

Embodiment 19 provides the method of any one of Embodiments 1-18,wherein the epoxy silane monomer has the structure:

wherein

-   -   at each occurrence, R¹ and R² are each independently chosen from        —H and substituted or unsubstituted (C₁-C₁₀)hydrocarbyl;    -   R³ is independently selected from —H, substituted or        unsubstituted (C₁-C₁₀)hydrocarbyl, and the structure:

-   -   R⁴ is independently chosen from —H and substituted or        unsubstituted (C₁-C₁₀)hydrocarbyl;    -   at each occurrence, J is independently selected from a bond and        substituted or unsubstituted (C₁-C₅)hydrocarbylene;    -   at each occurrence, L is independently chosen from substituted        or unsubstituted (C₁-C₁₀)hydrocarbylene interrupted or        terminated by 0, 1, 2, or 3 groups independently chosen from —O—        and —S—; and    -   c is about 0 to about 10.

Embodiment 20 provides the method of Embodiments 19, wherein at eachoccurrence, R¹ and R² are each independently chosen from —H and(C₁-C₁₀)alkyl.

Embodiment 21 provides the method of any one of Embodiments 19-20,wherein at each occurrence, R¹ and R² are each independently chosen from—H and (C₁-C₅)alkyl.

Embodiment 22 provides the method of any one of Embodiments 19-21,wherein at each occurrence, R¹ and R² are each independently chosen from—H and methyl.

Embodiment 23 provides the method of any one of Embodiments 19-22,wherein R³ is independently selected from —H and (C₁-C₁₀)alkyl.

Embodiment 24 provides the method of any one of Embodiments 19-23,wherein R³ is independently selected from —H and methyl.

Embodiment 25 provides the method of any one of Embodiments 19-24,wherein R⁴ is independently chosen from —H and (C₁-C₁₀)alkyl.

Embodiment 26 provides the method of any one of Embodiments 19-25,wherein R⁴ is independently chosen from —H and (C₁-C₅)alkyl.

Embodiment 27 provides the method of any one of Embodiments 19-26,wherein R⁴ is independently chosen from —H and methyl.

Embodiment 28 provides the method of any one of Embodiments 19-27,wherein at each occurrence J is independently chosen from a bond and a(C₁-C₅)alkylene.

Embodiment 29 provides the method of any one of Embodiments 19-24,wherein at each occurrence J is propylene.

Embodiment 30 provides the method of any one of Embodiments 19-29,wherein at each occurrence J is a bond.

Embodiment 31 provides the method of any one of Embodiments 19-30,wherein at each occurrence L is independently chosen from a substitutedor unsubstituted (C₁-C₁₀)hydrocarbylene interrupted or terminated by 0,1, 2, or 3 groups independently chosen from —O— and —S—.

Embodiment 32 provides the method of any one of Embodiments 19-31,wherein at each occurrence L is independently chosen from,(C₁-C₅)alkylene, —OCH₂(CH₂)₃CH₂—, —OCH₂(CH₂)₂CH₂—, —OCH₂CH₂CH₂—,—OCH₂CH₂—, and —OCH₂—.

Embodiment 33 provides the method of any one of Embodiments 19-32,wherein at each occurrence L is independently chosen from—OCH₂(CH₂)₃CH₂—, —OCH₂(CH₂)₂CH₂—, —OCH₂CH₂CH₂—, —OCH₂CH₂—, and —OCH₂—.

Embodiment 34 provides the method of any one of Embodiments 19-33,wherein at each occurrence L is —OCH₂—.

Embodiment 35 provides the method of any one of Embodiments 19-34,wherein c is about 0 to about 3.

Embodiment 36 provides the method of any one of Embodiments 19-35,wherein R³ at each occurrence independently has the structure:

wherein

-   -   at each occurrence, R² is independently chosen from —H and        (C₁-C₁₀)alkyl;    -   R⁴ is independently chosen from —H and (C₁-C₁₀)alkyl;    -   at each occurrence, J is independently chosen from a bond and a        (C₁-C₅)alkylene;    -   at each occurrence, L is independently chosen from        —OCH₂(CH₂)₃CH₂—, —OCH₂(CH₂)₂CH₂—, —OCH₂CH₂CH₂—, —OCH₂CH₂—, and        —OCH₂—; and    -   c is about 0 to about 5.

Embodiment 37 provides the method of any one of Embodiments 19-36,wherein R³ at each occurrence independently has the structure:

wherein

-   -   at each occurrence, R² is independently chosen from —H and        methyl;    -   R⁴ is independently chosen from —H and methyl;    -   at each occurrence, J is —CH₂CH₂H₂—;    -   at each occurrence, L is —OCH₂—; and        -   c is about 0 to about 3.

Embodiment 38 provides the method of any one of Embodiments 19-37,wherein the epoxy silane monomer has a structure chosen from

wherein

-   -   f is about 0 to about 6, and    -   at each occurrence R^(A) is independently chosen from —H and        —CH₃ and wherein the ratio of —H to —CH₃ is about 1 to 3 to        about 3 to 1.

Embodiment 39 provides the method of any one of Embodiments 1-38,wherein about 5 wt. % to about 50 wt. % of the curable composition isthe hardener.

Embodiment 40 provides the method of any one of Embodiments 1-39,wherein about 15 wt. % to about 35 wt. % of the curable composition isthe hardener.

Embodiment 41 provides the method of any one of Embodiments 1-40,wherein the hardener comprises at least one primary or secondary amine.

Embodiment 42 provides the method of any one of Embodiments 1-41,wherein the hardener comprises at least one of an amine, an aromaticamine, an aliphatic amine, a cyclo-aliphatic amine, a polyamine, anamide, and a polyamide.

Embodiment 43 provides the method of any one of Embodiments 1-42,wherein the hardener has the structure:

wherein

-   -   at each occurrence, R⁵ is independently chosen from substituted        or unsubstituted (C₁-C₁₀)hydrocarbylene;    -   at each occurrence, A is independently chosen from —O—, and        —NH—;    -   L² is independently chosen from a substituted or unsubstituted        (C₁-C₁₀)hydrocarbylene;    -   R⁶ is independently chosen from —NH₂, —Si(OR⁷)₃, and —OH,        wherein at each occurrence, R⁷ is independently chosen from a        (C₁-C₅)hydrocarbyl; and    -   i is about 1 to about 80.

Embodiment 44 provides the method of Embodiment 43, wherein at eachoccurrence R⁵ is independently chosen from (C₁-C₅)alkylene.

Embodiment 45 provides the method of any one of Embodiments 43-44,wherein at each occurrence R⁵ is independently chosen from —(CH₂)₂— and—CH(CH₃)CH₂—.

Embodiment 46 provides the method of any one of Embodiments 43-45,wherein at each occurrence L² is independently chosen from a substitutedor unsubstituted (C₁-C₁₀)hydrocarbylene.

Embodiment 47 provides the method of any one of Embodiments 43-46,wherein at each occurrence L² is independently chosen from —CH₂CH(CH₃)—and —(CH₂)₃—.

Embodiment 48 provides the method of any one of Embodiments 43-47,wherein at each occurrence R⁶ is independently chosen from —Si(OR⁷)₃,wherein at each occurrence R⁷ is independently chosen from —CH₃,—CH₂CH₃, and —(CH₂)₂CH₃.

Embodiment 49 provides the method of any one of Embodiments 43-48,wherein at each occurrence R⁶ is —Si(OCH₃)₃.

Embodiment 50 provides the method of any one of Embodiments 43-49,wherein i is about 1 to about 75.

Embodiment 51 provides the method of any one of Embodiments 1-50,wherein the hardener has a structure chosen from

wherein n is about 1 to about 80.

Embodiment 52 provides the method of Embodiment 51, wherein n is chosenfrom about 65 to about 75, about 28 to about 38, and about 4 to about 8.

Embodiment 53 provides the method of any one of Embodiments 43-48,wherein n is chosen from about 1 to about 3.

Embodiment 54 provides the method of any one of Embodiments 1-47,wherein the hardener comprises

wherein,

-   -   y is about 1 to about 45; and    -   x+z is about 1 to about 10.

Embodiment 55 provides the method of any one of Embodiments 43-48,wherein

-   -   y is about 1 to about 10; and    -   x+z is about 1 to about 5.

Embodiment 56 provides the method of any one of Embodiments 1-55,wherein the curable composition further comprises a silane couplingagent.

Embodiment 57 provides the method of any one of Embodiments 1-56,further comprising combining the curable composition with an aqueous oroil-based fluid comprising a drilling fluid, stimulation fluid,fracturing fluid, spotting fluid, clean-up fluid, completion fluid,remedial treatment fluid, abandonment fluid, pill, acidizing fluid,cementing fluid, packer fluid, logging fluid, or a combination thereof,to form a mixture, wherein the placing the curable composition in thesubterranean formation comprises placing the mixture in the subterraneanformation.

Embodiment 58 provides the method of any one of Embodiments 1-57,wherein at least one of prior to, during, and after the placing of thecurable composition in the subterranean formation, the curablecomposition is used in the subterranean formation, at least one of aloneand in combination with other materials, stimulation fluid, fracturingfluid, spotting fluid, clean-up fluid, completion fluid, remedialtreatment fluid, abandonment fluid, pill, acidizing fluid, cementingfluid, packer fluid, logging fluid, or a combination thereof.

Embodiment 59 provides the method of any one of Embodiments 1-58,wherein the curable composition further comprises saline, aqueous base,oil, organic solvent, synthetic fluid oil phase, aqueous solution,alcohol or polyol, cellulose, starch, alkalinity control agent, aciditycontrol agent, density control agent, density modifier, emulsifier,dispersant, polymeric stabilizer, crosslinking agent, polyacrylamide,polymer or combination of polymers, antioxidant, heat stabilizer, foamcontrol agent, solvent, diluent, plasticizer, filler or inorganicparticle, pigment, dye, precipitating agent, rheology modifier,oil-wetting agent, set retarding additive, surfactant, corrosioninhibitor, gas, weight reducing additive, heavy-weight additive, lostcirculation material, filtration control additive, salt, fiber,thixotropic additive, breaker, crosslinker, gas, rheology modifier,curing accelerator, curing retarder, pH modifier, chelating agent, scaleinhibitor, enzyme, resin, water control material, polymer, oxidizer, amarker, Portland cement, pozzolana cement, gypsum cement, high aluminacontent cement, slag cement, silica cement, fly ash, metakaolin, shale,zeolite, a crystalline silica compound, amorphous silica, fibers, ahydratable clay, microspheres, pozzolan lime, or a combination thereof.

Embodiment 60 provides the method of any one of Embodiments 1-59,wherein the placing of the curable composition in the subterraneanformation comprises fracturing at least part of the subterraneanformation to form at least one subterranean fracture.

Embodiment 61 provides the method of any one of Embodiments 1-60,wherein the curable composition further comprises a proppant, an epoxysilane resin-coated proppant, or a combination thereof.

Embodiment 62 provides the method of any one of Embodiments 1-61,wherein the placing of the curable composition in the subterraneanformation comprises pumping the curable composition through a tubulardisposed in a wellbore and into the subterranean formation.

Embodiment 63 provides a system for performing the method of any one ofEmbodiments 1-62, the system comprising:

a tubular disposed in the subterranean formation; and

a pump configured to pump the curable composition in the subterraneanformation through the tubular.

Embodiment 64 provides a method of treating a subterranean formation,the method comprising:

placing in a subterranean formation an curable composition comprising

-   -   an epoxy silane monomer having a structure chosen from

-   -   wherein about 40 wt. % to about 80 wt. % of the curable        composition is the epoxy silane monomer;

a hardener having a structure chosen from

-   -   wherein n is about 1 to about 5,    -   wherein about 5 wt. % to about 50 wt. % of the curable        composition is the hardener; and

a carrier fluid comprising water, wherein the carrier fluid is about 1wt. % to about 40 wt. % of the curable composition;

curing the curable composition to form an epoxy silane resin.

Embodiment 65 provides a method of treating a subterranean formation,the method comprising:

-   -   placing in a subterranean formation a curable composition        comprising        -   an epoxy monomer;        -   an amine silane hardener; and        -   a carrier fluid; and

curing the curable composition to form an epoxy silane resin.

Embodiment 66 provides the method of Embodiment 65, wherein the epoxymonomer has a structure chosen from:

wherein p is about 1 to about 200.

Embodiment 67 provides the method of any one of Embodiments 65-66,wherein the amine silane hardener has the structure:

Embodiment 68 provides the method of any one of Embodiments 65-67,wherein the carrier fluid comprises water.

Embodiment 69 provides a method of treating a subterranean formation,the method comprising:

placing in a subterranean formation a curable composition comprising

-   -   an epoxy monomer, wherein about 50 wt. % to about 70 wt. % of        the curable composition is the epoxy monomer;    -   an amine silane hardener having the structure

-   -   -   wherein about 20 wt. % to about 40 wt. % of the curable            composition is the amine silane hardener; and

    -   a carrier fluid comprising water, wherein the carrier fluid is        about 1 wt. % to about 40 wt. % of the curable composition, and

curing the curable composition to form an epoxy silane resin.

Embodiment 70 provides a system comprising:

an epoxy silane resin cured reaction product of a curable compositioncomprising

-   -   an epoxy silane monomer,    -   a hardener, and    -   a carrier fluid, and

a subterranean formation comprising the resin therein.

Embodiment 71 provides the system of Embodiment 70, further comprising

a tubular disposed in the subterranean formation; and

a pump configured to pump the curable composition in the subterraneanformation through the tubular.

Embodiment 72 provides a system comprising:

an epoxy silane resin cured reaction product of a curable compositioncomprising:

-   -   an epoxy monomer,    -   an amine silane hardener, and    -   a carrier fluid; and

a subterranean formation comprising the resin therein.

Embodiment 73 provides a composition for treatment of a subterraneanformation, the curable composition comprising:

an epoxy silane monomer;

a hardener; and

a carrier fluid.

Embodiment 74 provides the composition of Embodiment 73, wherein thecurable composition further comprises a downhole fluid.

Embodiment 75 provides the curable composition of any one of Embodiments73-74, wherein the curable composition is a composition for at least oneof remediating and consolidating a subterranean formation.

Embodiment 76 provides an epoxy silane resin cured reaction product ofthe curable composition of any one of Embodiments 73-75,

Embodiment 77 provides a curable composition for treatment of asubterranean formation, the curable composition comprising:

an epoxy silane monomer selected from

-   -   wherein about 55 wt. % to about 70 wt. % of the curable        composition is the epoxy silane monomer

a hardener selected from

-   -   wherein n is about 1 to about 4,    -   wherein about 15 wt. % to about 35 wt. % of the curable        composition is the hardener and

a carrier fluid comprising water, wherein about 5 wt. % to about 25 wt.% of the curable composition is the carrier fluid.

Embodiment 78 provides a curable composition for treatment of asubterranean formation, the curable composition comprising:

an epoxy monomer;

an amine silane hardener; and

a carrier fluid.

Embodiment 79 provides the curable composition of Embodiment 78, whereinthe curable composition comprises:

an epoxy monomer having a structure chosen from

-   -   wherein p is about 1 to about 200,    -   wherein about 55 wt. % to about 70 wt. % of the curable        composition is the epoxy monomer;

an amine silane hardener having the structure

and

a carrier fluid comprising water, wherein about 5 wt. % to about 25 wt.% of the curable composition is the carrier fluid.

Embodiment 80 provides a method of preparing a curable composition fortreatment of a subterranean formation, the method comprising:

forming a curable composition comprising

-   -   an epoxy silane monomer;    -   a hardener; and    -   a carrier fluid.

Embodiment 81 provides a method of preparing a curable composition fortreatment of a subterranean formation, the method comprising: forming acurable composition comprising

-   -   an epoxy monomer;    -   an amine silane hardener; and    -   a carrier fluid.

Embodiment 82 provides the composition, method, or system of any one orany combination of Embodiments 1-81 optionally configured such that allelements or options recited are available to use or select from.

What is claimed is:
 1. A curable composition for treatment of asubterranean formation, the curable composition comprising: an epoxymonomer and a hardener, wherein the epoxy monomer is an epoxy silanemonomer configured to be curable by the hardener; and a carrier fluid,wherein the epoxy monomer is an epoxy silane monomer selected from

wherein about 55 wt. % to about 70 wt. % of the curable composition isthe epoxy silane monomer; wherein the hardener is

wherein n is about 1 to about 4, wherein about 15 wt. % to about 35 wt.% of the curable composition is the hardener; and wherein the carrierfluid comprises water, wherein about 5 wt. % to about 25 wt. % of thecurable composition is the carrier fluid.
 2. The curable composition ofclaim 1, wherein the curable composition further comprises a downholefluid.
 3. The curable composition of claim 1, wherein the curablecomposition is a composition for at least one of remediating andconsolidating a subterranean formation.
 4. The curable composition ofclaim 1, wherein the curable composition is a composition for at leastone of cementing and plugging a subterranean formation.
 5. An epoxysilane resin cured reaction product of the curable composition ofclaim
 1. 6. The epoxy silane resin cured reaction product of claim 5,wherein the epoxy silane resin cured product is adhered to a casingdisposed in the subterranean formation.
 7. The curable composition ofclaim 1, wherein an epoxy silane resin reaction product of the curablecomposition is effective for adhering to a casing disposed in thesubterranean formation, thereby cementing or plugging the subterraneanformation.
 8. The curable composition of claim 1, wherein the carrierfluid comprises water including at least one of fresh water, brine,produced water, flowback water, brackish water, and sea water.
 9. Thecurable composition of claim 1, wherein the carrier fluid comprisescrude oil, dipropylene glycol methyl ether, dipropylene glycol dimethylether, dimethyl formamide, diethylene glycol methyl ether, ethyleneglycol butyl ether, diethylene glycol butyl ether, butylglycidyl ether,propylene carbonate, D-limonene, a C₂-C₄₀ fatty acid C₁-C₁₀ alkyl ester,tetrahydrofurfuryl methacrylate, tetrahydrofurfuryl acrylate, 2-butoxyethanol, butyl acetate, butyl lactate, furfuryl acetate, dimethylsulfoxide, dimethyl formamide, a petroleum distillation product offraction mineral oil, a hydrocarbon oil, a hydrocarbon including anaromatic carbon-carbon bond, a hydrocarbon including an alpha olefin,xylenes, an ionic liquid, methyl ethyl ketone, an ester of oxalic,maleic or succinic acid, methanol, ethanol, propanol, butyl alcohol, analiphatic hydrocarbon, or a combination thereof.
 10. The curablecomposition of claim 1, wherein an epoxy silane resin reaction productof the curable composition comprises reduced or eliminated segregationof epoxy and silane domains, increasing homogeneity and temperaturestability of the epoxy silane resin reaction product.
 11. The curablecomposition of claim 1, wherein an epoxy silane resin reaction productof the curable composition comprises a degradation onset between about300° F. and about 800° F.
 12. The curable composition of claim 1,wherein an epoxy silane resin reaction product of the curablecomposition comprises a peak degradation temperature between about 550°F. and about 850° F.
 13. The curable composition of claim 1, wherein anepoxy silane resin reaction product of the curable composition comprisesa ratio of epoxy functional groups to silane functional groups less thanabout 1 to
 1000. 14. The curable composition of claim 1, furthercomprising filler particles comprising aluminum oxide, awaruite, bariumcarbonate, barium oxide, barite, calcium carbonate, calcium oxide,cenospheres, chromite, chromium oxide, copper, copper oxide, dolomite,galena, hematite, hollow glass microspheres, ilmenite, iron oxide,siderite, magnetite, magnesium oxide, manganese carbonate, manganesedioxide, manganese (IV) oxide, manganese oxide, manganese tetraoxide,manganese (II) oxide, manganese (III) oxide, molybdenum (IV) oxide,molybdenum oxide, molybdenum trioxide, Portland cement, pumice, pyrite,spherelite, silica, silver, tenorite, titania, titanium (II) oxide,titanium (III) oxide, titanium (IV) dioxide, zirconium oxide, zirconiumsilicate, zinc oxide, cement-kiln dust, unexpanded and expanded perlite,attapulgite, bentonite, zeolite, elastomers, sand, micronized polymers,waxes, polymer fibers, inorganic fibers, and a combination thereof. 15.The curable composition of claim 1, further comprising a silane couplingagent comprising a (C₁-C₃₀)hydrocarbyl-substituted trimethoxysilane,N-2-(aminoethyl)-3-aminopropyltrimethoxysilane,3-glycidoxypropyltrimethoxysilane,n-beta-(aminoethyl)-gamma-aminopropyltrimethoxysilane, or a combinationthereof.
 16. The curable composition of claim 1, further comprising abreaker to at least partially break a fluid surrounding the curablecomposition.
 17. The curable composition of claim 1, further comprisinga viscosifier to increase a viscosity of the curable composition. 18.The curable composition of claim 1, further comprising a proppant, anepoxy silane resin-coated proppant, resin-coated proppant, anencapsulated epoxy silane resin, or a combination thereof.